Professional Documents
Culture Documents
A P P E N D I X
B
Information
for the Preliminary
Design of Fifteen
Chemical Processes
The purpose of the process designs contained in this appendix is to provide the reader
with a preliminary description of several common chemical processes. The designs pro-
vided are the result of preliminary simulation using the CHEMCAD process simulation
software and often contain simplifying assumptions such as ideal column behavior
(shortcut method using the Underwood-Gilliland method) and in some cases the use of
ideal thermodynamics models (K-value = ideal gas, enthalpy = ideal). These designs are
used throughout the book in the end-of-chapter problems and provide a starting point for
detailed design. The authors recognize that there are additional complicating factors,
such as nonideal phase equilibrium behavior (such as azeotrope formation and phase
separation), feed stream impurities, different catalyst selectivity, side reaction formation,
and so on. The presence of any one of these factors may give rise to significant changes
from the preliminary designs shown here. Thus, the student, if asked to perform a de-
tailed process design of these (or other) processes, should take the current designs as only
a starting point and should be prepared to do further research into the process to ensure
that a more accurate and deeper understanding of the factors involved is obtained.
Following is a list of the sections and projects discussed in this appendix:
61
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 62
DME is used primarily as an aerosol propellant. It is miscible with most organic solvents,
has a high solubility in water, and is completely miscible in water and 6% ethanol [1]. Re-
cently, the use of DME as a fuel additive for diesel engines has been investigated due to
its high volatility (desirable for cold starting) and high cetane number. The production of
DME is via the catalytic dehydration of methanol over an acid zeolite catalyst. The main
reaction is
2CH3OH → (CH3)2O + H2O (B.1.1)
methanol DME
In the temperature range of normal operation, there are no significant side reactions.
Vessel Preheater Cooler Tower Reboiler Condenser Reflux Pumps Reboiler Tower Condenser Reflux Pumps Cooler
Drum Drum
P-201A/B E-202 R-201
Feed Pump Reactor Reactor
Cooler
5/11/12
DME
Methanol 46 10
1 10.3 E-205
R-201
12:21 AM
2
12 121
6 FIC E-207
P-202A/B 7.3
9
P-201A/B FIC
22
3 5 cw
T-202
LIC
1
mps mps 139 17 LIC
V-203
E-201 8
7.4
E-202 TIC
11 14
cw 12
FIC
E-204 P-203A/B
4 7 26
E-203 LIC
mps
cw Wastewater
o
Temperature, C 14 15
Pressure, bar E-206
E-208
Figure B.1.1 Unit 200: Dimethyl Ether Process Flow Diagram
63
64
Turton_AppB_Part1.qxd
Stream Number 1 2 3 4 5 6 7 8
Temperature (°C) 25 25 45 154 250 364 278 100
Pressure (bar) 1.0 15.5 15.2 15.1 14.7 13.9 13.8 13.4
12:21 AM
Vapor fraction 0.0 0.0 0.0 1.0 1.0 1.0 1.0 0.0798
Mass flow (tonne/h) 8.37 8.37 10.49 10.49 10.49 10.49 10.49 10.49
Mole flow (kmol/h) 262.2 262.2 328.3 328.3 328.3 328.3 328.3 328.3
Page 64
Stream Number 9 10 11 12 13 14 15 16 17
Temperature (oC) 89 46 153 139 121 167 50 46 121
Pressure (bar) 10.4 11.4 10.5 7.4 15.5 7.6 1.2 11.4 7.3
Vapor fraction 0.148 0.0 0.0 0.04 0.0 0.0 0.0 0.0 0.0
Mass flow (tonne/h) 10.49 5.97 4.52 4.52 2.13 2.39 2.39 2.17 3.62
Mole flow (kmol/h) 328.3 129.7 198.6 198.6 66.3 132.3 132.3 47.1 113.0
Component flowrates (kmol/h)
Dimethyl ether 130.5 129.1 1.4 1.4 1.4 0.0 0.0 46.9 2.4
Methanol 64.9 0.6 64.3 64.3 63.6 0.7 0.7 0.2 108.4
Water 132.9 0.0 132.9 132.9 1.3 131.6 131.6 0.0 2.2
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 65
Heat Exchangers
E-201 E-205
A = 99.4 m2 A = 100.6 m2
Floating head, carbon steel, shell-and-tube design Fixed head, carbon steel, shell-and-tube design
Process stream in tubes Process stream in shell
Q = 14,400 MJ/h Q = 3140 MJ/h
Maximum pressure rating of 15 bar Maximum pressure rating of 10 bar
E-202 E-206
A = 171.0 m2 A = 83.0 m2
Floating head, carbon steel, shell-and-tube design Floating head, carbon steel, shell-and-tube design
Process stream in tubes and shell Process stream in shell
Q = 2030 MJ/h Q = 5790 MJ/h
Maximum pressure rating of 15 bar Maximum pressure rating of 11 bar
E-203 E-207
A = 101.8 m2 A = 22.7m2
Floating head, carbon steel, shell-and-tube design Floating head, carbon steel, shell-and-tube design
Process stream in shell Process stream in shell
Q = 12,420 MJ/h Q = 5960 MJ/h
Maximum pressure rating of 14 bar Maximum pressure rating of 7 bar
E-204 E-208
A = 22.0 m2 A = 22.8 m2
Floating head, carbon steel, shell-and-tube design Floating head, carbon steel, shell-and-tube design
Process stream in shell Process stream in shell
Q = 2490 MJ/h Q = 1200 MJ/h
Maximum pressure rating of 11 bar Maximum pressure rating of 8 bar
Pumps
P-201 A/B P-202 A/B
Reciprocating/electric drive Centrifugal/electric drive
Carbon steel Carbon steel
Power = 7.2 kW (actual) Power = 5.2 kW (actual)
60% efficient 40% efficient
Pressure out = 15.5 bar Pressure out = 16 bar
P-202 A/B
Centrifugal/electric drive
Carbon steel
Power = 1.0 kW (actual)
40% efficient
Pressure out = 11.4 bar
(continued)
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 66
T Kp
473 K (200°C) 92.6
573 K (300°C) 52.0
673 K (400°C) 34.7
The corresponding equilibrium conversions for pure methanol feed over the above tem-
perature range are greater than 99%. Thus this reaction is kinetically controlled at the con-
ditions used in this process.
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 67
The reaction takes place on an amorphous alumina catalyst treated with 10.2%
silica. There are no significant side reactions at less than 400°C. At greater than 250°C the
rate equation is given by Bondiera and Naccache [2] as:
− E0
− rmethanol k0 exp RT p methanol (B.1.2)
where k0 = 1.21 106 kmol/(m3cat.h.kPa), E0 = 80.48 kJ/mol, and pmethanol = partial pres-
sure of methanol (kPa).
Significant catalyst deactivation occurs at temperatures greater than 400°C, and the re-
actor should be designed so that this temperature is not exceeded anywhere in the reactor.
The design given in Figure B.1.1 uses a single packed bed of catalyst, which operates adia-
batically. The temperature exotherm occurring in the reactor of 118°C is probably on the
high side and gives an exit temperature of 368°C. However, the single-pass conversion is
quite high (80%), and the low reactant concentration at the exit of the reactor tends to limit
the possibility of a runaway.
In practice the catalyst bed might be split into two sections, with an intercooler be-
tween the two beds. This has an overall effect of increasing the volume (and cost) of the
reactor and should be investigated if catalyst damage is expected at temperatures lower
than 400°C. In-reactor cooling (shell-and-tube design) and cold quenching by splitting the
feed and feeding at different points in the reactor could also be investigated as viable al-
ternative reactor configurations.
B.1.4 References
1. “DuPont Talks about Its DME Propellant,” Aerosol Age, May and June 1982.
2. Bondiera, J., and C. Naccache, “Kinetics of Methanol Dehydration in Dealuminated
H-Mordenite: Model with Acid and Basic Active Centres,” Applied Catalysis 69
(1991): 139–148.
The majority of ethylbenzene (EB) processes produce EB for internal consumption within
a coupled process that produces styrene monomer. The facility described here produces
80,000 tonne/y of 99.8 mol% ethylbenzene that is totally consumed by an on-site styrene
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 68
facility. As with most EB/styrene facilities, there is significant heat integration between
the two plants. In order to decouple the operation of the two plants, the energy integra-
tion is achieved by the generation and consumption of steam within the two processes.
The EB reaction is exothermic, so steam is produced, and the styrene reaction is endother-
mic, so energy is transferred in the form of steam.
The reaction between EB and ethylene to produce DEB also takes place:
C6H5C2H5 + C2H4 → C6H4(C2H5)2 (B.2.2)
ethylbenzene ethylene diethylbenzene
Additional reactions between DEB and ethylene yielding triethylbenzene (and higher) are
also possible. However, in order to minimize these additional reactions, the molar ratio of
benzene to ethylene is kept high, at approximately 8:1. The production of DEB is undesir-
able, and its value as a side product is low. In addition, even small amounts of DEB in EB
cause significant processing problems in the downstream styrene process. Therefore, the
maximum amount of DEB in EB is specified as 2 ppm. In order to maximize the produc-
tion of the desired EB, the DEB is separated and returned to a separate reactor in which
excess benzene is added to produce EB via the following equilibrium reaction:
C6H4(C2H5)2 + C6H6 A 2C6H5C2H5 (B.2.3)
diethylbenzene benzene ethylbenzene
The incoming benzene contains a small amount of toluene impurity. The toluene reacts
with ethylene to form ethyl benzene and propylene:
C6H5CH3 + 2C2H4 → C6H5C2H5 + C3H6 (B.2.4)
toluene ethylbenzene propylene
i Ei ko,i a b c d e
kcal/kmol
1 22,500 1.00 × 106 1 0 0 1 0
2 22,500 6.00 × 105 1 1 0 0 0
3 25,000 7.80 × 106 0 0 0 1 1
4 20,000 3.80 × 108 2 0 1 0 0
The units of ri are kmol/s/m3-reactor, the units of Ci are kmol/m3-gas, and the units of ko,i
vary depending upon the form of the equation.
70
V-301 H-301 R-301/2/3 E-301/2 R-304 E-303 E-304 E-305 V-302 T-301 E-306 E-307 V-303 P-302 A/B T-302 E-308 E-309 V-304 P-303 A/B
Benzene Feed Ethylbenzene Reactor Trans- HP LP Reactor L/V Benzene Benzene Benzene Benzene Benzene EB EB EB EB EB
Feed Heater Reactors Inter- alkylation Steam Steam Effluent Separator To wer Reboiler Condenser Reflux Reflux To wer Reboiler Condenser Reflux Reflux
Turton_AppB_Part1.qxd
Drum coolers Reactor Boiler Boiler Cooler Drum Pumps Drum Pumps
P-301 A/B P-304 A/B P-305 A/B
Benzene DEB Benzene
Feed Recycle Recycle
Pumps Pumps Pumps
21 17
5/11/12
Benzene
1 2000 15
400 110
Fuel Gas
12:21 AM
8 11 T- 301
110
H-301
R-301 R-303 16 P-302 A/B
P-301 A/B
FIC
LIC
hps hps
7 9 12
E-303 E-304 E-305
4 hps lps
E-301 E-302
P-305 A/B bfw
80 E-306
bfw lps Ethylbenzene
5 14
10
19
2 bfw bfw cw
18 cw E-309
23
13
T- 302 P-303 A/B
LIC
R-304
°C
E-308
kPa hps
2000
20
H-301
P-304 A/B
Stream Number 7 8 9 10 11 12
Temperature (°C) 444.1 380.0 453.4 25.0 380.0 449.2
Pressure (kPa) 1970.0 1960.0 1945.0 2000.0 1935.0 1920.0
Vapor mole fraction 1.0 1.0 1.0 1.0 1.0 1.0
Total kg/h 18,797.9 19,784.7 19,784.7 986.8 20,771.5 20,771.5
Total kmol/h 234.0 269.0 236.4 35.0 271.4 238.7
Component Flowrates (kmol/h)
Ethylene 0.85 33.40 0.62 32.55 33.17 0.54
Ethane 2.10 4.55 4.55 2.45 7.00 7.00
Propylene 1.83 1.81 2.00 0.00 2.00 2.00
Benzene 203.91 203.91 174.96 0.00 174.96 148.34
Toluene 0.19 0.19 0.0026 0.00 0.0026 0.00
Ethylbenzene 24.28 24.28 49.95 0.00 49.95 70.57
1,4-Diethylbenzene 0.87 0.87 4.29 0.00 4.29 10.30
(continued)
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 72
Stream Number 13 14 15 16 17 18
Temperature (°C) 497.9 458.1 73.6 73.6 81.4 145.4
Pressure (kPa) 1988.0 1920.0 110.0 110.0 105.0 120.0
Vapor mole fraction 1.0 1.0 1.0 0.0 0.0 0.0
Total kg/h 4616.5 25,387.9 1042.0 24,345.9 13,321.5 11,024.5
Total kmol/h 51.3 290.0 18.6 271.4 170.2 101.1
Component Flowrates (kmol/h)
Ethylene 0.00 0.54 0.54 0.00 0.00 0.00
Ethane 0.00 7.00 7.00 0.00 0.00 0.00
Propylene 0.00 2.00 2.00 0.00 0.00 0.00
Benzene 29.50 177.85 8.38 169.46 169.23 0.17
Toluene 0.00 0.00 0.00 0.00 0.00 0.00
Ethylbenzene 21.69 92.25 0.71 91.54 0.92 90.63
1,4-Diethylbenzene 0.071 10.37 0.013 10.35 0.00 10.35
Stream Number 19 20 21 22 23
Temperature (°C) 139.0 191.1 82.6 82.6 121.4
Pressure (kPa) 110.0 140.0 2000.0 2000.0 2000.0
Vapor mole fraction 0.0 0.0 0.0 0.0 0.0
Total kg/h 9538.6 1485.9 10,190.9 3130.6 4616.5
Total kmol/h 89.9 11.3 130.2 40.0 51.3
Component Flowrates (kmol/h)
Ethylene 0.00 0.00 0.00 0.00 0.00
Ethane 0.00 0.00 0.00 0.00 0.00
Propylene 0.00 0.00 0.00 0.00 0.00
Benzene 0.17 0.00 129.51 39.78 39.78
Toluene 0.00 0.00 0.00 0.00 0.00
Ethylbenzene 89.72 0.91 0.70 0.22 1.12
1,4-Diethylbenzene 0.0001 10.35 0.00 0.00 10.35
lps to cw to hps to cw to
Stream Name E-306 tE-307 E-308* E-309
Flowrate (kg/h) 4362 174,100 3124 125,900
*
Throttled and desuperheated at exchanger
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 73
Fired Heater
H-301
Required heat load = 22,376 MJ/h
Design (maximum) heat load = 35,000
MJ/h
Tubes = Stainless steel
75% thermal efficiency
Maximum pressure rating of 2200 kPa
(continued)
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 74
Reactors
R-301 R-303
316 stainless steel packed bed, ZSM-5 316 stainless steel packed bed, ZSM-5
molecular sieve catalyst molecular sieve catalyst
V = 20 m3 V = 30 m3
11 m long, 1.72 m diameter 12 m long, 1.97 m diameter
Maximum pressure rating of 2200 kPa Maximum pressure rating of 2200 kPa
Maximum allowable catalyst temperature Maximum allowable catalyst temperature
= 500°C = 500°C
R-302 R-304
316 stainless steel packed bed, ZSM-5 316 stainless steel packed bed, ZSM-5
molecular sieve catalyst molecular sieve catalyst
V = 25 m3 V = 1.67 m3
12 m long, 1.85 m diameter 5 m long, 0.95 m diameter
Maximum pressure rating of 2200 kPa Maximum pressure rating of 2200 kPa
Maximum allowable catalyst temperature Maximum allowable catalyst temperature
= 500°C 525°C
Towers
T-301 T-302
Carbon steel Carbon steel
45 SS sieve trays plus reboiler and total 76 SS sieve trays plus reboiler and total
condenser condenser
42% efficient trays 45% efficient trays
Feed on tray 19 Feed on tray 56
Additional feed ports on trays 14 and 24 Additional feed ports on trays 50 and 62
Reflux ratio = 0.3874 Reflux ratio = 0.6608
24-in tray spacing 15-in tray spacing
Column height = 27.45 m Column height = 28.96 m
Diameter = 1.7 m Diameter = 1.5 m
Maximum pressure rating of 300 kPa Maximum pressure rating of 300 kPa
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 75
B.2.4 References
1. William J. Cannella, “Xylenes and Ethylbenzene,” Kirk-Othmer Encyclopedia of Chemi-
cal Technology, online version (New York: John Wiley and Sons, 2006).
2. “Ethylbenzene,” Encyclopedia of Chemical Processing and Design, Vol. 20, ed.
J. J. McKetta (New York: Marcel Dekker, 1984), 77–88.
Styrene is the monomer used to make polystyrene, which has a multitude of uses, the
most common of which are in packaging and insulated Styrofoam beverage cups. Styrene
is produced by the dehydrogenation of ethylbenzene. Ethylbenzene is formed by reacting
ethylene and benzene. There is very little ethylbenzene sold commercially, because most
ethylbenzene manufacturers convert it directly into styrene.
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 76
C6H5C2H5 →
3
C6H6 + C2H4 (B.3.2)
ethylbenzene benzene ethylene
C6H5C2H5 + H2 →
4
C6H5CH3 + CH4 (B.3.3)
ethylbenzene hydrogen toluene methane
ystyyhydP
K yeb (B.3.4)
14,852.6
In K 15.5408 −
T
where T is in K and P is in bar.
R-401 R-402 E-403 E-404 E-405 V-401 C-401 P-401a/b T-401 E-406 E-407 P-402a/b V-402 T-402 E-408 E-409
Turton_AppB_Part1.qxd
Styrene Styrene Product Product Product Three- Compressor Waste Benzene Reboiler Condenser Reflux Reflux Styrene Reboiler Condenser
Reactor Reactor Cooler Cooler Cooler Phase Water Toluene Pump Drum Column
Separator Pump Column
H-401 E-401 E-402 P-403 A/b P-404 A/b P-405 A/b P-406 A/b
Steam Feed Inter- Reflux Styrene Recycle Benzene/
Heater Heater Heater Pump Pump Pump Toluene
5/14/12
Pump
24
19
hps P-405 A/B
23
10:20 PM
1 2 3 7 Hydrogen
C-401
Ethylbenzene
E-401 6
26
17
Page 77
13 lps
10 15 18
E-407 P-403 A/B
E-403
bfw hps
cw LIC
bfw
11
Styrene
12 P-404 A/B
21
lps E-409 lps 20
E-404 E-405 P-401 A/B
22
Wastewater
77
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 78
Stream Number 6 7 8 9 10
Temperature (°C) 722.0 566.6 504.3 550.0 530.1
Pressure (kPa) 170.0 160.0 150.0 135.0 125.0
Vapor mole fraction 1.00 1.00 1.00 1.00 1.00
Total flow (kg/h) 54,045.0 78,010.2 78,010.2 78,010.2 78,010.2
Total flow (kmol/h) 3000.00 3226.21 3317.28 3317.28 3346.41
Component Flowrates (kmol/h)
Water 3000.00 3000.00 3000.00 3000.00 3000.00
Ethylbenzene 0.00 223.73 132.35 132.35 102.88
Styrene 0.00 0.06 91.06 91.06 120.09
Hydrogen 0.00 0.00 90.69 90.69 119.38
Benzene 0.00 1.21 1.28 1.28 1.37
Toluene 0.00 1.21 1.52 1.52 1.86
Ethylene 0.00 0.00 0.07 0.07 0.16
Methane 0.00 0.00 0.31 0.31 0.65
(continued)
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 79
Stream Number 16 17 18 19 20
Temperature (°C) 65.0 69.9 125.0 90.8 123.7
Pressure (kPa) 65.0 45.0 65.0 25.0 55.0
Vapor mole fraction 0.00 0.00 0.00 0.00 0.00
Total flow (kg/h) 23,709.6 289.5 23,420.0 10,912.9 12,507.1
Total flow (kmol/h) 226.21 3.34 222.88 102.79 120.08
Component Flowrates (kmol/h)
Water 0.00 0.00 0.00 0.00 0.00
Ethylbenzene 102.88 0.10 102.78 102.73 0.05
Styrene 120.09 0.00 120.09 0.06 120.03
Hydrogen 0.00 0.00 0.00 0.00 0.00
Benzene 1.37 1.37 0.00 0.00 0.00
Toluene 1.86 1.86 0.00 0.00 0.00
Ethylene 0.00 0.00 0.00 0.00 0.00
Methane 0.00 0.00 0.00 0.00 0.00
Stream Number 21 22 23 24 25
Temperature (°C) 123.8 65.0 202.2 91.0 800.0
Pressure (kPa) 200.0 200.0 140.0 200.0 4202.0
Vapor mole fraction 0.00 0.00 1.00 0.00 1.00
Total flow (kg/h) 12,507.1 54,045.0 255.6 10,912.9 18,308.7
Total flow (kmol/h) 120.08 3000.00 120.20 102.79 1016.30
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 80
Stream Number 26
Temperature (°C) 70.0
Pressure (kPa) 200.00
Vapor mole fraction 0.00
Total flow (kg/h) 289.5
Total flow (kmol/h) 3.34
Component Flowrates (kmol/h)
Water 0.00
Ethylbenzene 0.10
Styrene 0.00
Hydrogen 0.00
Benzene 1.37
Toluene 1.86
Ethylene 0.00
Methane 0.00
Heat Exchangers*
E-401 E-406
Carbon steel Carbon steel
A = 260 m2 A = 173 m2
Boiling in shell, condensing in tubes Process fluid in shell, cooling water in tubes
1 shell––2 tube passes 1 shell––2 tube passes
Q = 13,530 MJ/h Q = 12,951 MJ/h
E-402 E-407
316 stainless steel Carbon steel
A = 226 m2 A = 64 m2
Boiling in shell, process fluid in tubes Steam in shell, steam condensing in tubes
1 shell––2 tube passes Desuperheater––steam saturated at 150°C
Q = 8322 MJ/h 1 shell––2 tube passes
E-403 Q = 15,742 MJ/h
316 stainless steel E-408
A = 1457 m2 Carbon steel
Boiling in shell, process fluid in tubes A = 385 m2
1 shell––2 tube passes Process fluid in shell, cooling water in tubes
Q = 44,595 MJ/h 1 shell––2 tube passes
E-404 Q = 46,274 MJ/h
Carbon steel E-409
A = 702 m2 Carbon steel
Boiling in shell, process fluid in tubes A = 176 m2
1 shell––2 tube passes Boiling in shell, steam condensing in tubes
Q = 13,269 MJ/h Desuperheater––steam saturated at 150°C
E-405 1 shell––2 tube passes
316 stainless steel Q = 45,476 MJ/h
A = 1446 m2
cw in shell, process fluid in tubes
1 shell––2 tube passes
Q = 136,609 MJ/h
Fired Heater
H-401
Fired heater-refractory-lined, stainless-steel tubes
Design Q = 23.63 MW
Maximum Q = 25.00 MW
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 82
Reactors
R-401 R-402
316 stainless steel, packed bed 316 stainless steel, packed bed
Cylindrical catalyst pellet (1.6 mm 3.2 mm) Cylindrical catalyst pellet (1.6 mm 3.2 mm)
Void fraction = 0.4 Void fraction = 0.4
V = 25 m3 V = 25 m3
9.26 m tall, 1.85 m diameter 9.26 m tall, 1.85 m diameter
Towers
T-401 T-402
Carbon steel Carbon steel
D = 3.0 m D = 6.9 m
61 sieve trays 158 bubble cap trays
54% efficient 55% efficient
Feed on tray 31 Feed on tray 78
12-in tray spacing 6-in tray spacing
1-in weirs 1-in weirs
Column height = 61 ft = 18.6 m Column height = 79 ft = 24.1 m
Vessels
V-401 V-403
Carbon steel Horizontal
V = 26.8 m3 Carbon steel
L/D = 3
V = 5 m3
V-402
Horizontal
Carbon steel
L/D = 3
V = 5 m3
* See Figure B.3.1 and Table B.3.1 for shell- and tube-side pressures.
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 83
21,708
r1 10.177 1011 exp − peb (B.3.6)
RT
RT p p
7804
r2 20.965 exp sty hyd
(B.3.7)
exp −
RT
49675
r3 7.206 1011 p eb
(B.3.8)
26857
r4 1.724 106 exp − peb phyd (B.3.9)
RT
where p is in bar, T is in K, R = 1.987 cal/mol K, and ri is in mol/m3-reactor s.
You should assume that the catalyst has a bulk density of 1282 kg/m3, an effective
diameter of 25 mm, and a void fraction = 0.4.
B.3.4 References
1. Shiou-Shan Chen, “Styrene,” Kirk-Othmer Encyclopedia of Chemical Technology, online
version (New York: John Wiley and Sons, 2006).
2. “Styrene,” Encyclopedia of Chemical Processing and Design, Vol. 55, ed. J. J. McKetta,
(New York: Marcel Dekker, 1984), 197–217.
3. Snyder, J. D., and B. Subramaniam, “A Novel Reverse Flow Strategy for Ethyl-
benzene Dehydrogenation in a Packed-Bed Reactor,” Chem. Engr. Sci. 49 (1994):
5585–5601.
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 84
Drying oils are used as additives to paints and varnishes to aid in the drying process
when these products are applied to surfaces. The facility manufactures drying oil (DO)
from acetylated castor oil (ACO). Both of these compounds are mixtures. However, for
simulation purposes, acetylated castor oil is modeled as palmitic (hexadecanoic) acid
(C15H31COOH) and drying oil is modeled as 1-tetradecene (C14H28). In an undesired side
reaction, a gum can be formed, which is modeled as 1-octacosene (C28H56).
where
− r1 k1CACO (B.4.3)
− r2 k2C2DO (B.4.4)
and
k1 5.538 1013 exp(− 44,500RT) (B.4.5)
The units of reaction rate, ri, are kmol/m3s, and the activation energy is in cal/mol (which
is equivalent to kcal/kmol).
Turton_AppB_Part1.qxd
V-501 P-501 A/B H-501 R-501 E-501 V-502 A/B T-501 E-502 E-503 P-502 A/B V-503 T-502 E-504 E-505 P-503 A/B V-504 E-506 P-504 A/B
Recycle Feed Feed Drying Reactor Gum ACO Recyle Recyle Recycle Recycle Drying Drying Drying Oil Drying Oil Drying Recycle Recycle
Mixing Pump Fired Oil Effluent Filter Recycle Tower Tower Tower Tower Oil Oil Tower Tower Oil Cooler Pump
Vessel Heater Reactor Cooler Holding Tower Reboiler Condenser Reflux Reflux Tower Tower Condenser Reflux Tower
Vessel Pump Drum Reboiler Pump Reflux
Drum
5/11/12
Acetylated
Castor Oil
1
11
FIC E-505
12:21 AM
V-501 H-501
cw Acetic
V-502 A/B Acid
3
T-502 FIC LIC
2 V-504
9
Page 85
7 E-504 12
R-501 P-502 A/B hps
Drying
LIC Oil
E-502
6
Dowtherm A
14 lps from H-501
5 10
E-501 Gum
lps
bfw
E-506
13
P-504 A/B
bfw
85
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 86
Stream Number 5 6 7 8
Temperature (°C) 342.8 175.0 175.0 175.0
Pressure (kPa) 183.0 148.0 136.0 136.0
Vapor mole fraction 0.39 0.00 0.00 0.00
Flowrate (kg/h) 10,703.1 10,703.1 10,703.1 0.02
Flowrate (kmol/h) 48.07 48.07 48.07 4.61 × 10-5
Component flowrates (kmol/h)
Acetic acid 6.32 6.32 6.32 0.00
1-Tetradecene (drying oil) 6.38 6.38 6.38 0.00
Hexadecanoic acid (ACO) 35.38 35.38 35.38 0.00
Gum 4.61 × 10-5 4.61 × 10-5 0.00000 4.61 × 10-5
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 87
Stream Number 13 14
Temperature (°C) 170.0 170.0
Pressure (kPa) 65.0 110.0
Vapor mole fraction 0.00 0.00
Flowrate (kg/h) 9074.4 9074.4
Flowrate (kmol/h) 35.40 35.40
Component flowrates (kmol/h)
Acetic acid 0.00 0.00
1-Tetradecene (drying oil) 0.06 0.06
Hexadecanoic acid (ACO) 35.34 35.34
Gum 0.00 0.00
Pumps
P-501 A/B P-503 A/B
Centrifugal/electric drive Centrifugal/electric drive
Carbon steel Stainless steel
Power = 0.9 kW (actual) Power = 0.8 kW (actual)
80% efficient 80% efficient
NPSHR at design flow = 14 ft of liquid
P-504 A/B
P-502 A/B Stainless steel/electric drive
Centrifugal/electric drive Power = 0.3 kW (actual)
Stainless steel 80% efficient
Power = 1 kW (actual) NPSHR at design flow = 12 ft of liquid
80% efficient
Reactor
R-501
Stainless steel vessel
V = 1.15 m3
5.3 m long, 0.53 m diameter
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 89
Vessels
V-501 V-503
Horizontal Horizontal
Carbon steel Stainless steel
L/D = 3 L/D = 3
V = 2.3 m3 V = 2.3 m3
V-502 V-504
Vertical Horizontal
Stainless steel Carbon steel
L/D = 5 L/D = 3
V = 3 m3 V = 0.3 m3
B.4.4 Reference
1. Smith, J. M., Chemical Engineering Kinetics, 3rd ed. (New York: John Wiley and Sons,
1981), 224–228.
Currently, the preferred route to maleic anhydride in the United States is via isobutene in
fluidized-bed reactors. However, an alternative route via benzene may be carried out
using a shell-and-tube reactor, with catalyst in the tubes and a cooling medium being cir-
culated through the shell [1, 2].
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 90
k
C6H6 4.5O2 S C4H2O3 2CO2 2H2O
1
(B.5.1)
benzene maleic anhydride
k2
C6H6 7.5O2 S 6CO2 3H2O (B.5.2)
benzene
k4
C6H6 1.5O2 S C6H4O2 2H2O (B.5.4)
benzene quinone
All the reactions are highly exothermic. For this reason, the ratio of air to benzene
entering the reactor is kept very high. A typical inlet concentration (Stream 6) of approxi-
mately 1.5 vol% of benzene in air is used. Cooling is achieved by circulating molten salt (a
mixture of sodium nitrite and sodium nitrate) cocurrently through the shell of the reactor
and across the tubes containing the catalyst and reactant gases. This molten salt is cooled
in two external exchangers—E-602 and E-607—prior to returning to the reactor.
The reactor effluent, Stream 7—containing small amounts of unreacted benzene,
maleic anhydride, quinone, and combustion products—is cooled in E-603 and then sent
to an absorber column, T-601, which has both a reboiler and condenser. In T-601, the
vapor feed is contacted with recycled heavy organic solvent (dibutyl phthalate), Stream 9.
This solvent absorbs the maleic anhydride, quinone, and small amounts of water. Any
water in the solvent leaving the bottom of the absorber, T-601, reacts with the maleic an-
hydride to form maleic acid, which must be removed and purified from the maleic anhy-
dride. The bottoms product from the absorber is sent to a separation tower, T-602, where
the dibutyl phthalate is recovered as the bottoms product, Stream 14, and recycled back to
the absorber. A small amount of fresh solvent, Stream 10, is added to account for losses.
The overhead product from T-602, Stream 13, is sent to the maleic acid column, T-603,
where 95 mol% maleic acid is removed as the bottoms product.
The overhead stream is taken to the quinone column, T-604, where 99 mol%
quinone is taken as the top product and 99.9 mol% maleic anhydride is removed as the
bottoms product. These last two purification columns are not shown in Figure B.5.1 and
are not included in the current analysis.
Stream summaries, utility summaries, and equipment summaries are presented in
Tables B.5.1–B.5.3.
V-601 C-601 P-601A/B E-601 H-601 P-602 A/B E-602 R-601 P-603A/B E-603 T- 601 E-604 V-602 P-604 A/B E-605
Benzene Inlet Air Benzene Benzene Feed Molten Molten Reactor Dibutyl Reactor MA MA Tower MA MA MA
Feed Compressor Feed Feed Heater Salt Circ. Salt Makeup Effluent Scrubber Condenser Reflux Reflux Reboiler
Turton_AppB_Part1.qxd
P-603 A/B
5
12:21 AM
Air
FIC
4
Products of
116 Combustion
C-601 9 E-604 Off-Gas to
Incinerator
Page 91
H-601
~
E-601
cw 12
PIC ~
lps
T- 601
LIC V-602
6
Benzene air ng
3 FIC
1 P-604A/B E-606
R-601 E-605
15 LIC
V-601 FIC
hps T- 602 cw
E-602
2 hps
hps
16 8 FIC LIC To Maleic
V-603
7 Anhydride
P-601 A/B
Purification
11
bfw
~ 13
P-602 A/B E-603 P-605A/B ~
Temperature °C bfw
E-607 LIC
14
P-606 A/B
91
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 92
Stream Number 9 10 11 12 13 14 15 16
Temperature (°C) 330 320 194 84 195 330 419 562
Pressure (kPa) 82 100 82 75 80 82 200 200
Total kg/h 139,191.6 30.6 141,866 81,225 2597 139,269 391,925 391,925
Total kmol/h 500.1 0.1 526.2 2797.9 26.2 500.0 5000.0 5000.0
Component Flowrates (kmol/h)
Maleic anhydride 0.0 0.0 4.8 0.5 24.8 0.0 0.0 0.0
Dibutyl phthalate 500.1 0.1 500.0 0.0 0.0 500.0 0.0 0.0
Nitrogen 0.0 0.0 0.0 2205.0 0.0 0.0 0.0 0.0
Water 0.0 0.0 0.0 91.5 0.0 0.0 0.0 0.0
Oxygen 0.0 0.0 0.0 370.2 0.0 0.0 0.0 0.0
Benzene 0.0 0.0 0.0 2.6 0.0 0.0 0.0 0.0
Quinone 0.0 0.0 0.4 0.4 0.4 0.0 0.0 0.0
Carbon dioxide 0.0 0.0 0.0 129.0 0.0 0.0 0.0 0.0
Maleic acid 0.0 0.0 1.0 0.0 1.0 0.005 0.0 0.0
Sodium nitrite 0.0 0.0 0.0 0.0 0.0 0.0 2065.6 2065.6
Sodium nitrate 0.0 0.0 0.0 0.0 0.0 0.0 2934.4 2934.4
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 93
(continued)
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 94
The units of reaction rate, ri, are kmol/m3(reactor)s, the activation energy is given in
cal/mol (which is equivalent to kcal/kmol), the units of ki are m3(gas)/m3 (reactor)s, and
the units of concentration are kmol/m3(gas).
The catalyst is a mixture of vanadium and molybdenum oxides on an inert support.
Typical inlet reaction temperatures are in the range of 350°C to 400°C. The catalyst is
placed in 25 mm diameter tubes that are 3.2 m long. The catalyst pellet diameter is 5 mm.
The maximum temperature that the catalyst can be exposed to without causing
irreversible damage (sintering) is 650°C. The packed-bed reactor should be costed as a
shell-and-tube exchanger. The heat transfer area should be calculated based on the total
external area of the catalyst-filled tubes required from the simulation. Because of the high
temperatures involved, both the shell and the tube material should be stainless steel. An
overall heat transfer coefficient for the reactor should be set as 100 W/m2°C. (This is the
value specified in the simulation.)
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 96
B.5.4 References
1. Felthouse, T. R., J. C. Burnett, B. Horrell, M. J. Mummey, and Y-J Kuo, “Maleic Anhy-
dride, Maleic Acid, and Fumaric Acid,” Kirk-Othmer Encyclopedia of Chemical Technol-
ogy, online version (New York: John Wiley and Sons, 2001).
2. “Maleic Acid and Anhydride,” Encyclopedia of Chemical Processing and Design, Vol.
29, ed. J. J. McKetta (New York: Marcel Dekker, 1984), 35–55.
3. Wohlfahrt, Emig G., “Compare Maleic Anhydride Routes,” Hydrocarbon Processing,
June 1980, 83–90.
Ethylene oxide is a chemical used to make ethylene glycol (the primary ingredient in an-
tifreeze). It is also used to make polyethylene oxide, and both the low-molecular-weight
and high-molecular-weight polymers have many applications including as detergent addi-
tives. Because ethylene oxide is so reactive, it has many other uses as a reactant. However,
because of its reactivity, danger of explosion, and toxicity, it is rarely shipped outside the
manufacturing facility but instead is often pumped directly to a nearby consumer.
Compressor cooler Compressor Reactor Cooler Absorber Preheater Reactor Cooler Absorber Precooler Column
C-702 E-702 E-703 E-709 V-701 P-701 A/B
Air Inter- Reactor Reboiler Reflux Reflux
Compressor cooler Preheater Drum Pump
5/11/12
E-704 E-706
C-704 C-705 27
20 21
12 13
Fuel
22 Gas
12:21 AM
cw cw
24 26
23
15
Process
mps 14 mps Light
Water
Page 97
Gases
34
16
T-702
R-701 R-702
E-705
E-709
hps cw
19 T-703
T-701
18
25 E-707 FIC LIC
V-701
bfw bfw
17 29 30 31
28
P-701A/B
32
cw
LIC Ethylene
2 8 9 Oxide
11
Ethylene
33
Air
C-701 cw C-702 cw C-703 hps
97
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 98
Stream Number 5 6 7 8
Temperature (°C) 206.1 45.0 195.2 –6.3
Pressure (bar) 9.0 8.7 27.0 27.0
Vapor mole fraction 1.00 1.00 1.00 1.00
Flowrate (kg/h) 500,000 500,000 500,000 20,000
Flowrate (kmol/h) 17,381.45 17,381.45 17,381.45 712.91
Component flowrates (kmol/h)
Ethylene 0.0 0.0 0.0 712.91
Ethylene oxide 0.0 0.0 0.0 0.0
Carbon dioxide 0.0 0.0 0.0 0.0
Oxygen 3281.35 3281.35 3281.35 0.0
Nitrogen 14,100.09 14,100.09 14,100.09 0.0
Water 0.0 0.0 0.0 0.0
Stream Number 9 10 11 12
Temperature (°C) 26.3 106.7 240.0 240.0
Pressure (bar) 27.0 26.8 26.5 25.8
Vapor mole fraction 1.00 1.00 1.00 1.00
Flowrate (kg/h) 524,042 1,023,980 1,023,980 1,023,979
Flowrate (kmol/h) 18,260.29 35,639.59 35,639.59 35,539.42
Component flowrates (kmol/h)
Ethylene 1047.95 1047.91 1047.91 838.67
Ethylene oxide 6.48 6.47 6.47 206.79
Carbon dioxide 31.71 31.71 31.71 49.56
Oxygen 3050.14 6331.12 6331.12 6204.19
Nitrogen 14,093.02 28,191.39 28,191.39 28,191.39
Water 30.99 30.98 30.98 48.82
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 99
Stream Number 17 18 19 20
Temperature (°C) 51.9 240.0 239.9 240.0
Pressure (bar) 30.0 29.7 26.5 25.8
Vapor mole fraction 0.00 1.00 1.00 1.00
Flowrate (kg/h) 368,611 1,015,669 1,015,669 1,015,669
Flowrate (kmol/h) 20,181.77 35,357.65 35357.66 35,277.47
Component flowrates (kmol/h)
Ethylene 0.70 837.96 837.96 670.64
Ethylene oxide 191.34 15.45 15.45 175.83
Carbon dioxide 0.01 49.55 49.55 63.44
Oxygen 1.45 6202.74 6202.74 6101.72
Nitrogen 2.68 28,188.72 28,188.72 28,188.72
Water 19,985.58 63.24 63.24 77.13
(continued)
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 100
100 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
Stream Number 25 26 27 28
Temperature (°C) 52.3 30.1 30.1 29.5
Pressure (bar) 30.0 30.0 30.0 27.0
Vapor mole fraction 0.00 1.00 1.00 1.00
Flowrate (kg/h) 367,885 504,042 504,042 504,042
Flowrate (kmol/h) 20,182.72 17,547.38 17,547.38 17,547.38
Component flowrates (kmol/h)
Ethylene 0.57 335.04 335.04 335.04
Ethylene oxide 162.88 6.48 6.48 6.48
Carbon dioxide 0.01 31.71 31.71 31.71
Oxygen 1.43 3050.14 3050.14 3050.14
Nitrogen 2.68 14,093.02 14,093.02 14,093.02
Water 20,015.15 30.99 30.99 30.99
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 101
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 101
Stream Number 33 34
Temperature (°C) 182.3 86.4
Pressure (bar) 10.5 10.0
Vapor mole fraction 0.00 1.00
Flowrate (kg/h) 720,703 278.78
Flowrate (kmol/h) 40,002.57 9.53
Component flowrates (kmol/h)
Ethylene 0.0 1.27
Ethylene oxide 2.18 0.0
Carbon dioxide 0.0 0.02
Oxygen 0.0 2.88
Nitrogen 0.0 5.35
Water 40,000.39 0.0
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 102
102 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
*Note that all compressors have electric-explosion-proof drives with a backup. These units are
designated D-701 A/B through D-705 A/B but are not shown on the PFD.
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 103
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 103
Pump
P-701 A/B
Centrifugal/electric drive
Stainless steel
Power = 4 kW (actual)
75% efficient
Reactors
R-701 R-702
Carbon steel, shell-and-tube packed bed Carbon steel, shell-and-tube packed bed
Spherical catalyst pellet, 9 mm diameter Spherical catalyst pellet, 9 mm diameter
Void fraction = 0.4 Void fraction = 0.4
V = 202 m3 V = 202 m3
10 m tall, 7.38 cm diameter tubes 10 m tall, 9.33 cm diameter tubes
4722 tubes 2954 tubes
100% filled with active catalyst 100% filled with active catalyst
Q = 33,101 MJ/h Q = 26,179 MJ/h
mps made in shell mps made in shell
(continued)
Turton_AppB_Part1.qxd 5/11/12 12:21 AM Page 104
104 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
stream is purged, with the remainder recycled to recover unreacted ethylene. The com-
bined aqueous product streams are mixed, cooled, throttled, and distilled to produce the
desired product. The required purity specification is 99.5 wt% ethylene oxide.
Stream summary tables, utility summary tables, and major equipment specifications
are shown in Tables B.6.1–B.6.3.
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 105
The units for the reaction rates are moles/m3 s. The pressure unit is bar. The activation
energy numerator is in cal/mol. The catalyst used for this reaction is silver on an inert
support. The support consists of 7.5 mm diameter spheres that have a bulk density of
1250 kg/m3 and a void fraction of 0.4.
• K-values: Use a global model of PSRK but use UNIFAC as a local model for T-701
and T-702.
• Enthalpy: Use SRK.
B.6.4 References
1. Dever, J. P., K. F. George, W. C. Hoffman, and H. Soo, “Ethylene Oxide,” Kirk-Oth-
mer Encyclopedia of Chemical Technology, online version (New York: John Wiley and
Sons, 2004).
2. “Ethylene Oxide,” Encyclopedia of Chemical Processing and Design, Vol. 20, ed. J. J.
McKetta (New York: Marcel Dekker, 1984), 274 –318.
3. Stoukides, M., and S. Pavlou, “Ethylene Oxidation on Silver Catalysts: Effect of Eth-
ylene Oxide and of External Transfer Limitations,” Chem. Eng. Commun. 44 (1986):
53–74.
The reactor is a unique configuration, in which the silver catalyst is in the form of wire
gauze, suspended above a heat exchanger tube bank. Because the net reaction is very
106
C-801 P-801 A/B E-801 E-802 R-801 T-801 T-802 E-803 E-804 E-805 V-801 P-802 A/B P-803 A/B E-806
Turton_AppB_Part1.qxd
Feed Air Methanol Methanol Air Formaldehyde Formaldehyde Formaldehyde Reactor Tower Tower Tower Tower Product Product
Compressor Feed Pump Preheater Preheater Reactor Absorber Tower Effluent Reboiler Condenser Reflux Reflux Pump Cooler
Cooler Drum Pump
5/11/12
18
Deionized
12
Water
11 Off-Gas
12:22 AM
E-801
4
2 3 T-801 14
Page 106
E-802
E-805
TIC
1 5 7 8 cw
10
Air LIC FIC
C-801 hps V-801 LIC
T-802
cw 13
9 P-802 A/B
bfw
E-803
LIC
E-806
16 17
E-804 15
mps Formalin
cw
P-803 A/B to Storage
Tank
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 107
exothermic, the heat generated in the adiabatic reactor section must be removed quickly,
hence the close proximity of the heat-exchanger tubes. The heat exchanger resembles a pool
boiler, with a pool of water on the shell side. If the temperature of the effluent is too high,
the set point on the steam pressure line is lowered to increase the vaporization of boiler feed
water (bfw). In general, the liquid-level controller on the bfw is adjusted to keep the tube
bundle fully immersed. The reactor effluent enters an absorber in which most of the
methanol and formaldehyde are absorbed into water, with most of the remaining light
gases purged into the off-gas stream. The methanol, formaldehyde, and water enter a distil-
lation column, in which the methanol overhead is recycled; the bottoms product is a
formaldehyde/water mixture that contains ≤1 wt% methanol as an inhibitor. This mixture
is cooled and sent to a storage tank, which is sized at four days’ capacity. This storage tank
is essential, because some of the downstream processes are batch. The composition in the
storage tank exceeds 37 wt% formaldehyde, so the appropriate amount of water is added
when the downstream process draws from the storage tank. This is not shown in the PFD
(Figure B.7.1).
Storage of formaldehyde/water mixtures is tricky. At high temperatures, undesir-
able polymerization of formaldehyde is inhibited, but formic acid formation is favored.
At low temperatures, acid formation is inhibited, but polymerization is favored. There are
stabilizers that inhibit polymerization, but they are incompatible with resin formation.
Methanol, at concentrations between 5 wt% and 15 wt%, can also inhibit polymerizaton,
but no separation equipment for methanol currently exists on site, and methanol greater
than 1 wt% also causes defective resin production. With ≤1 wt% methanol, the storage
tank contents must be maintained between 35°C and 45°C.
Stream summary tables, utility summary tables, and major equipment specifications
are shown in Tables B.7.1–B.7.3.
108 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
Stream Number 7 8 9 10 11 12
Temperature (°C) 200.0 171.9 200.0 100.0 30.0 84.6
Pressure (kPa) 265.0 255.0 185.0 150.0 150.0 140.0
Vapor fraction 1.0 1.0 1.0 1.0 0.0 1.0
Total kmol/h 4210.5 7330.8 7330.8 7330.8 2576.2 5354.2
Total kg/h 145.94 245.86 278.03 278.03 143.00 224.16
Component flowrates (kmol/h)
Methanol 0.0 94.12 31.45 31.45 0.0 13.35
Oxygen 30.66 30.66 0.15 0.15 0.0 0.15
Formaldehyde 0.0 0.0 62.67 62.67 0.0 0.04
Water 0.0 5.81 66.82 66.82 143.00 93.68
Hydrogen 0.0 0.0 1.66 1.66 0.0 1.66
Nitrogen 115.28 115.28 115.28 115.28 0.0 115.28
Turton_AppB_Part1.qxd 5/11/12 12:22 AM Page 109
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 109
110 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
Compressor
C-801 D-801 A/B (not shown on PFD)
Carbon steel Electric/explosion proof
Centrifugal W = 195 kW
Power = 183 kW (shaft) 95% efficient
70% efficient
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 111
When simulating an entire process, it is recommended to first use the Shortcut dis-
tillation column within the process for the methanol-water/formaldehyde distillation. A
rigorous column solver should then be used as a separate item to simulate the column
based on the results obtained from the Shortcut column. However, due to the nonideality
of the thermodynamics, the actual column simulation using the rigorous column will
probably require many more stages than predicted by the shortcut simulation, possibly
twice the number. Once the parameters for the rigorous column have been established,
the Shortcut column can be replaced by the rigorous column and the simulation rerun to
get a converged simulation.
112 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
B.7.4 References
1. Gerberich, H. R., and G. C. Seaman, “Formaldehyde,” Kirk-Othmer Encyclopedia of
Chemical Technology, online version (New York: John Wiley and Sons, 2004).
2. “Formaldehyde,” Encyclopedia of Chemical Processing and Design, Vol. 23, ed.
J. J. McKetta (New York: Marcel Dekker, 1984), 350–371.
3. Gmehling, J., U. Onken, and W. Arlt, Vapor-Liquid Equilibrium Data Collection, Chem-
istry Data Series (Aqueous-Organic Systems, Supplement 1), Vol. 1, Part 1a,
DECHEMA, 1981, 474–475.
Phenlyalanine and L-aspartic acid are amino acids. When they bond together, the corre-
sponding di-peptide methyl ester is aspartame, known by the brand name NutraSweet or
Equal. Production of both amino acids can be accomplished via fermentation of geneti-
cally altered bacteria. Production rates of 1000 and 1250 tonnes/y of L-aspartic acid and
L-phenylalanine are desired.
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 113
The use of batch processing requires batch scheduling of the type discussed in Chap-
ter 3, which allows use of the same equipment to manufacture both amino acids in the same
facility. In this description, only the PFD, reactor calculations, and general descriptions of
the separation units are presented. The design of individual equipment, the utility con-
sumption, and the production schedule for the plant are left as exercises for the student. A
description of a process to produce four amino acids (including the two amino acids in this
process) in the same facility is available at http://www.che.cemr.wvu.edu/publications/
projects/large_proj/batch-production_of_amino_acids.pdf. This process description in-
cludes possible batch schedules for both the reactors and the separation section.
The bacteria cells are suspended in a matrix polyacrylamide gel, and the reacting species
must diffuse in and out of the matrix. The diffusivities of the substrate (fumaric acid) and
product (L-aspartic acid) in the gel decrease as their concentrations increase due to the
tendency of the gel to shrink at low pH.
The kinetic model for this reaction follows a Michaelis-Menten form for a reversible
reaction, which rearranges to
1 1 Ka,M
(B.8.2)
Va Va,max CAA
Va,max CFA −
KCNH 4
Reaction rate parameters have been modified from reference [1] and are used for the cur-
rent process using a 1.0 M substrate solution at a reaction temperature of 32°C.
Ka,M 0.68C1.04
FA,0
0.77
CFA,0
Va,max
150
K 88.7 m kmol at 32°C
3
CNH4 2.04CFA
V-901 T-901 CR-901 E-901 E-902
114
F-901-3 R-901 F-904 P-901 F-905
Sterilization Fermenter Bacteria Slurry Ion Exchange Product Reflux Waste- Crystallizer Amino Acid
Storage Crystallizer Heater water
Turton_AppB_Part1.qxd
Inoculation F-901
1 2 F-904 Vent
5/11/12
11 12
1
Nutrient Feed F-902
3 4
TIC
12:22 AM
cw R-901
lps
pHIC
13
1
Page 114
F-904
F-903 Bacteria
6
1
14
1
Air
5
15
1
Ammonia
7 8 E-902 Waste-
V-901 water
21 22
1
Sulfuric Acid
9 10 16
1 cw
CR-901
20
1
Elutant E-901
Amino Acid
F-905 Crystals
17 T-901 23
26 27
24 lps
25
28
1
P-901 Nutrient
19 Solution
18
1
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 115
It should be noted that the relationship CNH4 2.04CFA can be achieved only in a batch re-
actor by measuring the concentration of fumaric acid and adjusting the ammonia concen-
tration with time. This approach is assumed here; however, if a fixed amount of ammonia
is initially added to the reactor, then the relationship between CNH4 and CFA must be
found from the material balance and substituted in Equation (B.8.2).
Substituting the above values into Equation (B.8.2) and using the conversion, X, of
fumaric acid (CFA = CFA,0(1 – X) and CAA = CFA,0X), we get
C0.77 (1 − 2X)
VCFA,0 dX
Va FA,0 (B.8.3)
W dt 150 1 − (2 123C1.04
FA,0)X 123CFA,0
1.04
(1 − e)rbead (1 − 2X)
dX
(B.8.4)
dt CFA,0150 (1 123CFA,0) − (2 123C1.04
0.23 1.04
FA,0)X
For the specified initial concentration of fumaric acid of 1.0M = 1 kmol/m3 and with
rbead ~ 1000 kg/m3 and assuming a voidage of 0.5, Equation (B.8.4) simplifies to
(1 − 2X)
dX
3.33 (B.8.5)
dt 124 − 125X
Separating variables and integrating Equation (B.8.5) yield the conversion as a function of
batch reaction time. This relationship is shown in Figure B.8.2.
Conversion of Fumaric Acid, X
116 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
dX mS
X (B.8.6)
dt Ks S
dS 1 mmS
= - X (B.8.7)
dt YXS Ks + S
dP YPS mmS
= X (B.8.8)
dt YXS Ks + S
According to Tsuchida et al. [2], for a culture medium containing 13% glucose,
1% ammonium sulfate, and 1.2% fumaric acid (plus other trace nutrients, etc.) the yield
of L-phenylalanine was 21.7 mg/ml after 72 h of cultivation at a temperature of 31.5°C.
This represents a yield of approximately 16.7% from glucose by weight. Other amino
acids are also produced in small quantities (<5 kg/m3), with lysine making up approxi-
mately 50%.
To obtain a kinetic model of the growth of bacteria and subsequent production of
L-phenylalanine and depletion of glucose, the parameters in Equations (B.8.6)–(B.8.8)
were back-calculated to give best-fit profiles of X, S, and P compared to published values
([2], Figure 4). The parameter values are shown in Table B.8.1, and the profiles are plotted
in Figure B.8.3.
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 117
Using a 37.9 m3 (10,000 gal) reactor for the fermentation and assuming that a 90% fill
volume is used, the volume of reactants is (37.9)(0.9) = 34.11 m3.
The amount of L-phenylalanine produced in a 60 h batch reaction is (34.11)(21.0) =
716 kg.
Production rate of L-aspartic acid from a 10,000 gallon reactor is 716 kg/
batch, with a reactor step time of 65 h.
Filtration of Bacteria. After reaction, the bacteria must be filtered from the mother
liquor prior to storage. The bacteria tend to give rise to slimy filter cakes, and the filtration
of such material is best accomplished using a rotary drum filter utilizing a precoat. Typical
P
X
Reaction Time, h
118 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
precoating materials are dolomite, perlite, and cellulose, and these are applied to the drum
in a two-stage process prior to filtration. The precoating process involves depositing a
layer of the precoat material (5–15 cm thick) on the drum prior to the filtration operation.
Once the precoat has been applied, the filtration starts, and the biomass forms a thin layer
on the precoat. This layer of biomass is continuously removed, along with a thin layer of
the precoat material, using a sharp-edged “Doctor” blade. Additional information is given
at http://www.solidliquid-separation.com [3]. Without doing detailed calculations, it is
difficult to determine the time required for the precoat stage and filtration stages. For this
project you may assume that these steps take 25 h and 5 h, respectively.
Ion Exchange Column. The ion exchange columns operate as semibatch processes.
Hydrochloric acid is added to the L-phenylalanine-containing solution and is passed
through freshly regenerated ion exchange resin such as Dow’s DOWEX MARATHON C
[4]. The resin captures the positively charged amino acid. Once the bed is full, it is back-
washed with a basic solution of ammonium or sodium hydroxide, which breaks the resin
amino acid bond. The resin is subsequently washed free of the hydroxide, and the cycle
starts again.
Continuous Crystallizer and Filtration. Draft tube baffle crystallizers can be used
for the crystallization of L-aspartic acid and L-phenylalanine. These crystallizers offer the
advantages of high circulation rates for efficient mixing. Fines removal is facilitated
through the use of baffles, and a certain amount of product classification (crystal size con-
trol) is obtained through the elutriating leg. Batch crystallizers could also be used, but
product quality and efficiency suffer. The saturated liquid from the crystallizer, contain-
ing amino acid crystals, is sent to a filter (such as a rotary drum filter), where the crystals
are removed and sent for washing, drying, and packaging. The saturated liquid is re-
turned to the crystallizer for further product recovery, thereby increasing the efficiency of
the operation. Both amino acids can be crystallized at temperatures greater than 100°C.
Therefore, the crystallization may take place at ambient pressure by removing the excess
water through evaporation. The solubilities of L-aspartic acid and L-phenylalanine at
100°C are 67 g/liter and 100 g/liter, respectively.
B.8.3 References
1. Takamatch, T., K. Yamashita, and A. Sumi, “Kinetics of Production of L-Aspartic
Acid by Aspartase of Immobilized E. Coli Cells,” Japanese Journal of Fermentation
Technology 58, no. 2 (1980): 129–133.
2. Tsuchida, T., K. Kubota, Y. Morinaga, H. Matsui, H. Enei, and F. Yoshinga, “Produc-
tion of L-Phenylalanine by a Mutant of Brevibacterium lactofermentum 2256,” Agric.
Bio. Chem. 51, no. 8 (1987): 2095–2101.
3. http://www.solidliquid-separation.com.
4. DOWEX MARATHON C data sheet, http://www.dow.com/PublishedLiterature/
dh_0082/0901b80380082af5.pdf?filepath=liquidseps/pdfs/noreg/177-
01593.pdf&fromPage=GetDoc.
Turton_AppB_Part1.qxd 5/11/12 12:22 AM Page 119
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 119
Acrylic acid (AA) is used as a precursor for a wide variety of chemicals in the polymer
and textile industries. There are several chemical pathways to produce AA, but the most
common one is via the partial oxidation of propylene. The usual mechanism for produc-
ing AA utilizes a two-step process in which propylene is first oxidized to acrolein and
then further oxidized to AA. Each reaction step usually takes place over a separate cata-
lyst and at different operating conditions. The reaction stoichiometry is given below:
C3H6 O2 → C3H4O H2O
acrolein
1
C3H4O O → C3H4O2
2 2
acrylic acid
Several side reactions may occur, most resulting in the oxidation of reactants and prod-
ucts. Some typical side reactions are given below:
7
C3H4O O → 3CO2 2H2O
2 2
3
C3H4O O2 → C2H4O2 CO2
2
acetic acid
9
C3H6 O → 3CO2 3H2O
2 2
Therefore, the typical process setup consists of a two-reactor system, with each reactor
containing a separate catalyst and operating at conditions so as to maximize the produc-
tion of AA. The first reactor typically operates at a higher temperature than the second.
As with any reaction involving the partial oxidation of a fuel-like feed material
(propylene), considerable attention must be paid to the composition of hydrocarbons and
oxygen in the feed stream. In the current design, a fluidized-bed reactor is used, which
provides essentially isothermal conditions in the reactor and, with the addition of large
amounts of steam, allows safe and stable operation. The second safety concern is associ-
ated with the highly exothermic polymerization of AA, which occurs in two ways. First, if
this material is stored without appropriate additives, then free radical initiation of the
polymerization can occur. This potentially disastrous situation is discussed by Kurland
and Bryant [1]. Second, AA dimerizes when in high concentrations at temperatures
greater than 90°C, and thus much of the separation sequence must be operated under
high vacuum in order to keep the bottom temperatures in the columns below this
temperature.
120 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
C-1001A/B E-1001 P-1001A/B R-1001 T-1001 T-1002 P-1002A/B E-1002 T-1003 E-1009 T-1004 E-1003 E-1004
Inlet Air Molten Salt Molten Salt Reactor Quench Off-Gas Quench Quench Acid Solvent Solvent Solvent Solvent
Blower Cooler Circ. Pumps Tower Absorber Pumps Cooler Extractor Exchgr Tower Reboiler Condsr
Deionized Water 11
FIC
T-1002 22
E-1009 T-1003
10
1
cw
9 1
R-1001
15 23
T-1001
200
5.0 40
1 cw
2.4
7 FIC
FIC 5
Air
FIC 8
15
E-1001
Steam C-1001A/B 6
FIC
cw
2 E-1002
12
P-1001A/B
191
Propylene FIC
4.3
3 4 50
P-1002A/B
310
3.5
Figure B.9.1 Unit 1000: Production of Acrylic Acid from Propylene PFD (The
point where Streams 1 and 2 are mixed with Stream 3 to form Stream 4 actually
occurs within Reactor R-1001.)
the products of reaction quickly to avoid further oxidation reactions, and this is achieved
by rapidly quenching the reactor effluent with a cool recycle, Stream 8, of dilute aqueous
AA in T-1001. Additional recovery of AA and acetic acid (a by-product) is achieved in the
absorber, T-1002. The stream leaving the absorption section is a dilute aqueous acid,
Stream 9. This is sent to a liquid-liquid extractor, T-1003, to remove preferentially the acid
fraction from the water prior to purification. There are many possible solvents that can be
used as the organic phase in the separation; high solubility for AA and low solubility for
water are desirable. Some examples include ethyl acrylate, ethyl acetate, xylene, di-
isobutyl ketone, methyl isobutyl ketone, and diisopropyl ether (DIPE), which is used
here. The organic phase from T-1003 is sent to a solvent recovery column, T-1004, where
the diisopropyl ether (and some water) is recovered overhead and returned to the extrac-
tor. The bottom stream from this column, Stream 14, contains virtually all the AA and
acetic acid in Stream 9. This is sent to the acid purification column, T-1005, where 95% by
mole acetic acid by-product is produced overhead, and 99.9% by mole AA is produced as
a bottoms product and cooled prior to being sent to storage.
The aqueous phase from the extractor, Stream 12, is sent to a wastewater column,
T-1006, where a small amount of DIPE is recovered overhead and returned to the extrac-
tor. The bottoms product, containing water and trace quantities of solvent and acid, is
sent to wastewater treatment. Process stream information and preliminary equipment
summaries are given in Tables B.9.1 and B.9.2, respectively. A utility summary is also
provided in Table B.9.3.
Turton_AppB_Part1.qxd 5/11/12 12:22 AM Page 121
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 121
P-1003A/B P-1004A/B V-1001 T-1005 E-1005 E-1006 P-1005A/B V-1002 T-1006 E-1007 E-1008 P-1006A/B V-1003 P-1007A/B E-1010
Acid Solvent Solvent Acid Acid Acid Acid Acid Waste Waste Waste Waste Waste Product Product
Feed Reflux Reflux Tower Reboiler Condsr Reflux Reflux Tower Reboiler Condsr Reflux Reflux Pumps Cooler
Pumps Pumps Drum Pumps Drum Pumps Drum
Off-Gas to Incinerator
13 47
T-1004 T-1005
0.12 0.07 19
T-1006 Acetic Acid
E-1004 60
E-1006 1.0
16
1
rw cw E-1008
13 15
18 1
cw
V-1001 LIC
V-1002 LIC 21
23 FIC
FIC
V-1003 FIC
FIC
36 6
LIC
LIC
P-1005 A/B 8
lps
P-1004 A/B lps LIC
P-1006 A/B
lps
14
17 20
E-1003 E-1005
P-1003 A/B E-1007 To Wastewater Treatment
40
1.1
o
Acrylic Acid
Temperature, C cw
Pressure, bar P-1007 A/B E-1010 TBWS Designs - Acrylic Acid Process
Drawn by Date
Checked by Date
Approved by Date
5
C3H6 O → C2H4O2 CO2 H2O Reaction 2
2 2
acetic acid
9
C3H6 O → 3CO2 3H2O Reaction 3
2 2
Ei
where − ri ko,i exp − p p
RT propylene oxygen
122
Turton_AppB_Part1.qxd
5/11/12
Stream Number 1 2 3 4 5 6 7 8 9
12:22 AM
Mole flow (kmol/h) 1362.9 992.3 127.0 2482.2 0.00 2444.0 148.5 85,200.0 1249.6
Component flowrates HiTec
(kmol/h) Molten Salt
Propylene 0.00 0.00 127.0 127.0 0.00 14.7 0.00 0.00 0.00
Nitrogen 1056.7 0.00 0.00 1056.7 0.00 1056.7 0.00 0.00 0.00
Oxygen 280.9 0.00 0.00 280.9 0.00 51.9 0.00 0.00 0.00
Carbon dioxide 0.00 0.00 0.00 0.00 0.00 60.5 0.00 0.00 0.00
Water 25.3 992.3 0.00 1017.6 0.00 1165.9 140.9 78,870 1156.7
Acetic acid 0.00 0.00 0.00 0.00 0.00 6.54 0.65 415 6.08
Acrylic acid 0.00 0.00 0.00 0.00 0.00 87.79 6.99 5915 86.81
Solvent
(diisopropyl ether) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Turton_AppB_Part1.qxd
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Stream Number 10 11 12 13 14 15 16 17 18
12:22 AM
Temperature (°C) 25 48 40 40 90 13 13 89 47
Pressure (bar) 5.0 1.0 2.4 2.4 0.19 0.12 3.0 0.16 0.07
Vapor fraction 0.0 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Mass flow (tonne/h) 2.54 37.35 20.87 143.0 6.63 155.3 136.4 6.26 5.28
Page 123
Mole flow (kmol/h) 141.0 1335.4 1156.9 1591.2 93.19 1705.7 1498.0 86.85 90.49
Component flowrates
(kmol/h)
Propylene 0.00 14.7 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Nitrogen 0.00 1056.7 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Oxygen 0.00 51.9 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Carbon dioxide 0.00 60.5 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Water 141.0 150.2 1156.6 198.8 0.30 226.0 198.5 0.00 4.28
Acetic acid 0.00 0.46 0.03 6.08 6.08 0.00 0.00 0.05 86.07
Acrylic acid 0.00 0.98 0.00 86.81 86.81 0.00 0.00 86.80 0.14
Solvent
(diisopropyl ether) 0.00 0.00 0.30 1299.5 0.00 1479.7 1299.5 0.00 0.00
(continued)
123
124
Turton_AppB_Part1.qxd
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Stream Number 19 20 21 22 23
12:22 AM
(continued)
125
126
Turton_AppB_Part1.qxd
5/11/12
Equipment P-1001 A/B P-1002 A/B P-1003 A/B P-1004 A/B P-1005 A/B P-1006 A/B P-1007 A/B
Table B.9.2 Preliminary Equipment Summary Table for Unit 1000 (Continued)
127
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128 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
Table B.9.2 Preliminary Equipment Summary Table for Unit 1000 (Continued)
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 129
Partial pressures are in kPa, and the activation energies and preexponential terms for re-
actions 1–3 are as follows:
Ei ko,i
i kcal/kmol kmol/m3 reactor h/(kPa)2
1 15,000 1.59 × 105
2 20,000 8.83 × 105
3 25,000 1.81 × 108
The reactor configuration used for this process is a fluidized bed, and it is assumed that
the bed of catalyst behaves as a well-mixed tank—that is, it is isothermal at the tempera-
ture of the reaction (310°C). The gas flow is assumed to be plug flow through the bed,
with 10% of the gas bypassing the catalyst. This latter assumption is made in order to sim-
ulate the gas channeling that occurs in real fluid-bed reactors.
B.9.4 References
1. Kurland, J. J., and D. B. Bryant, “Shipboard Polymerization of Acrylic Acid,” Plant
Operations Progress 6, no. 4 (1987): 203–207.
2. Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed., Vol. 1 (New York: John
Wiley and Sons, 1978), 330–354.
3. Encyclopedia of Chemical Processing and Design, ed. J. J. McKetta and W. A. Cunning-
ham, Vol. 1 (New York: Marcel Dekker, 1976), 402–428.
4. Sakuyama, S., T. Ohara, N. Shimizu, and K. Kubota, “A New Oxidation Process for
Acrylic Acid from Propylene,” Chemical Technology, June 1973, 350.
5. “1986 Student Contest Problem,” The AIChE Student Annual 1986, ed. B. Van Wie
and R. A. Wills (AIChE, 1986), 52–82.
The prevalent process for the production of acetone is as a by-product of the manufacture
of phenol. Benzene is alkylated to cumene, which is further oxidized to cumene hy-
droperoxide and finally cleaved to yield phenol and acetone. However, the process
shown in Figure B.10.1 and discussed here uses isopropyl alcohol (IPA) as the raw
Turton_AppB_Part1.qxd 5/11/12 12:22 AM Page 130
130 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
V-1101 P-1101A/B E-1101 R-1101 E-1102 E-1103 P-1102A/B H-1101 V-1102 T-1101
IPA Feed IPA Feed IPA Feed IPA Reactor Trim Reactor Reactor Phase Acetone
Drum Pumps Vaporizer Reactor Effluent Cooler Cooler Heater Pumps Furnace Separator Stripper
FIC 7
hps
234 8
Isopropyl Alcohol 2.16
407 H-1101
2 2.66
E-1101
1 FIC
T-1101
R-1101
4
V-1101 LIC 357
3.00 air ng
TIC P-1102A/B 5
45 20
cw 1.77 rw 1.63
3
P-1101A/B 6
V-1102
E-1102 E-1103
14
Figure B.10.1 Unit 1100: Production of Acetone from Isopropyl Alcohol PFD
material. This is a viable commercial alternative, and a few plants continue to operate
using this process. The primary advantage of this process is that the acetone produced is
free from trace aromatic compounds, particularly benzene. For this reason, acetone pro-
duced from IPA may be favored by the pharmaceutical industry due to the very tight re-
strictions placed on solvents by the Food and Drug Administration (FDA). The reaction to
produce acetone from IPA is as follows:
(CH3)2CHOH → (CH3)2CO H2
isopropyl alcohol acetone
The reaction conditions are typically 2 bar and 350°C, giving single-pass conversions of
85%–92%.
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 131
T-1102 E-1104 V-1103 E-1105 P-1103A/B P-1104A/B T-1103 E-1106 E-1107 V-1104 P-1105A/B E-1108
Acetone Acetone Acetone Acetone Acetone IPA IPA IPA IPA IPA IPA Waste-
Column Overhead Reflux Reboiler Reflux Column Column Overhead Reboiler Reflux Reflux water
Condenser Drum Pumps Pumps Condenser Drum Pumps Cooler
16
cw
61 E-1104 Hydrogen
PIC
1.20
11
cw
1 E-1106
FIC V-1103 LIC Acetone
T-1102 T-1103
1
10 V-1104 LIC
FIC
33 13
P-1103 A/B
E-1105 66
16
LIC P-1105 A/B
lps E-1107 19
LIC cw 45
1.26
lps
12 15
to remove the excess water from the unused IPA, which is then recycled back to the front
end of the process as an azeotropic mixture. Stream summaries, preliminary equipment,
and utility summaries are given in Tables B.10.1, B.10.2, and B.10.3, respectively.
Ea kmol
− rIPA k0 exp − C
RT IPA m3reactor s
m3gas kmol
where Ea 72.38MJkmol, k0 3.51 105 3 , CIPA 3
m reactor s m gas
In practice, several side reactions can occur to a small extent. Thus, trace quantities of
propylene, diisopropyl ether, acetaldehyde, and other hydrocarbons and oxides of carbon
Turton_AppB_Part1.qxd 5/11/12 12:22 AM Page 132
132 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
can be formed [1]. The noncondensables are removed with the hydrogen, and the aldehy-
des and ethers may be removed with acid washing or adsorption. These side reactions are
not accounted for in this preliminary design.
For the design presented in Figure B.10.1, the reactor was simulated with catalyst in
2-in (50.4 mm) diameter tubes, each 20 ft (6.096 m) long, and with a cocurrent flow of a
heat transfer medium on the shell side of the shell-and-tube reactor. The resulting
arrangement gives a 90% conversion of IPA per pass.
B.10.4 References
1. Kirk-Othmer Encyclopedia of Chemical Technology, 3d ed., Vol. 1 (New York: John
Wiley and Sons, 1976), 179–191.
2. Shreve’s Chemical Process Industries, 5th ed., ed. G. T. Austin (New York: McGraw-
Hill, 1984), 764.
3. Encyclopedia of Chemical Processing and Design, Vol. 1, ed. J. J. McKetta and W. A.
Cunningham (New York: Marcel Dekker, 1976), 314–362.
4. Sheely, C. Q., Kinetics of Catalytic Dehydrogenation of Isopropanol, Ph.D. Thesis, Uni-
versity of Illinois, 1963.
The background information for this process is taken from Chauvel et al. [1]. This
example is an illustration of a preliminary estimate of a process to convert a mixture
of C3 and C4 unsaturated hydrocarbons to 1-heptene and other unsaturated products.
The market for the 1-heptene product would be as a highoctane blending agent for
gasoline or in the production of plasticizers. Based on preliminary market estimates, a
production capacity of 20,000 metric tons per year of 1-heptene using 8000 operating
hours/y was set. This process differs from the other examples in Appendix B in sev-
eral ways. First, the raw materials to the process contain a wide variety of chemicals.
This is typical for oil refinery and some petrochemical operations. Second, no specific
kinetic equations are given for the reactions. Instead, the results of laboratory tests
using the desired catalyst at different conditions and using different feed materials are
used to guide the process engineer to an optimum, or close to an optimum, reactor
configuration. The flowsheet in Figure B.11.1 and stream, equipment summary, and
utility summary tables, Tables B.11.1–B.11.3, have been developed using such infor-
mation. It should be noted that a preliminary economic analysis, and hence the feasi-
bility of the process, can be determined without this information, as long as yield and
conversion data are available and the reactor configuration can be estimated.
Turton_AppB_Part1.qxd
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Stream Number 1 2 3 4 5 6 7 8
Temperature (oC) 25 32 350 357 20 27 33 25
Page 133
Pressure (bar) 1.01 2.30 1.91 3.0 1.63 1.63 1.50 2.0
Vapor fraction 0.0 0.0 1.0 0.0 1.0 0.0 1.0 0.0
Mass flow (tonne/h) 2.40 2.67 2.67 35.1 0.34 0.46 0.24 0.36
Mole flow (kmol/h) 51.96 57.84 92.62 0.00 39.74 21.14 38.60 20.00
Component flowrates Molten
(kmol/h) Salt
Hydrogen 0.00 0.00 34.78 0.00 34.78 0.00 34.78 0.00
Acetone 0.00 0.16 34.94 0.00 4.44 1.93 2.51 0.00
Isopropyl alcohol 34.82 38.64 3.86 0.00 0.12 0.10 0.02 0.00
Water 17.14 19.04 19.04 0.00 0.40 19.11 1.29 20.00
(continued)
133
134
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12:22 AM
Stream Number 9 10 11 12 13 14 15 16
Temperature (oC) 22 61 61 90 83 83 109 33
Page 134
Pressure (bar) 1.63 1.5 1.5 1.4 1.2 1.2 1.4 1.2
Vapor fraction 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.0
Mass flow (tonne/h) 2.79 4.22 1.88 0.92 8.23 0.27 0.65 0.24
Mole flow (kmol/h) 74.02 72.51 32.29 41.73 177.18 5.88 35.85 38.60
Component flowrates
(kmol/h)
Hydrogen 0.00 0.00 0.00 0.00 0.00 0.00 0.00 34.78
Acetone 32.43 72.46 32.27 0.16 4.82 0.16 0.00 2.51
Isopropyl alcohol 3.84 0.05 0.02 3.82 115.10 3.82 0.00 0.02
Water 37.75 0.00 0.00 37.75 57.26 1.90 35.85 1.29
Turton_AppB_Part1.qxd
Equipment P-1101 A/B P-1102 A/B P-1103 A/B P-1104 A/B P-1105 A/B V-1101 V-1102
MOC Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel
12:22 AM
Power (shaft)
(kW) 0.43 2.53 1.75 0.06 1.45 0.00 0.00
Efficiency 40% 50% 40% 40% 40% 0.00 0.00
Type/drive Centrifugal/ Centrifugal/ Centrifugal/ Centrifugal/ Centrifugal/ 0.00 0.00
Page 135
(continued)
135
136
Turton_AppB_Part1.qxd
5/11/12
Table B.10.2 Preliminary Equipment Summary Table for Unit 1100 (Continued)
Duty (MJ/h) 3550 3260 563 3095 3500 7340 7390 174
Area (m2) 70.3 77.6 8.5 39.1 30.9 50.2 65.1 1.6
Shell side
Page 137
137
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138 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
V-1201 P-1201A/B V-1202 R-1201 E-1201 A-E P-1202 A-G E-1202 T-1201 E-1203 V-1203 P-1203 A/B
E-1204
Propylene Butene Butene Heptene Reactor Reactor Reactor C3/C4 C3/C4 C3/C4
C3/C4 C3/C4
Feed Tank Feed Pumps Feed Tank Reactor Intercoolers Pumps Effluent Tower Reboiler Overhead Reflux Reflux
Heater Condensr Drum Pumps
3
R-1201
Catalyst Makeup FIC
7
45
5.50 cw
E-1204
PIC
TIC
C 3 Feed cw 6
T-1201
1 LIC
FIC V-1203
1 TIC
cw 103
5.80 5
V-1201 FIC
TIC 11
P-1203 A/B
cw
C 4 Feed E-1203 20
TIC
cw lps LIC
2
TIC
FIC
cw
V-1202 8
P-1202 A-G E-1201 A-E
Figure B.11.1 Unit 1200: Production of Heptenes from Propylene and Butenes PFD
Turton_AppB_Part1.qxd 5/11/12 12:22 AM Page 139
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 139
T-1202 E-1205 P-1204 A/B E-1206 V-1204 P-1205 A/B E-1207 T-1203 E-1208 E-1209 E-1210 E-1211 V-1205 P-1206 A/B
C6 C6 C7/C8 Feed C6 C6 C6 Reflux C7 C7 C7 C6 C7 C8 C7 Reflux C7 Reflux
Tower Reboiler Pumps Ovhd Reflux Pumps Product Tower Reboiler Ovhd Prod Prod Drum Pumps
Condsr Drum Cooler Condsr Cooler Cooler
C3 Fuel Gas
C4 to LPG
cw E-1207 45
78 E-1206 1.70 Hexenes
2.00
107 cw
cw E-1209
1.50
1 V-1204 LIC
FIC
T-1202
45
1 V-1205 cw 1.20
10 FIC LIC
9 Heptenes
13
20 T-1203 12
P-1205 A/B
24 E-1210
E-1205 38 P-1206 A/B
LIC E-1208 41
lps
LIC
lps E-1211 45
cw 1.70
C 8 + Heavies
11 14
o
P-1204 A/B Temperature, C
Pressure, bar TBWS Designs - Heptenes Process
Drawn by Date
Checked by Date
Approved by Date
140 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
Stream Number 1 2 3 4 5 6 7
Temperature (oC) 25 25 26 45 45 45 45
Pressure (bar) 11.6 3.0 8.0 7.7 7.5 6.5 5.0
Vapor fraction 0.0 0.0 0.0 0.0 0.0 0.0 1.0
Mass flow (tonne/h) 3.15 9.29 12.44 12.44 3.68 6.66 0.13
Mole flow (kmol/h) 74.57 163.21 237.78 178.10 64.41 116.45 3.00
Component flowrates
(kmol/h)
Propane 3.56 0.00 3.56 3.56 0.31 0.56 3.00
Propylene 71.06 0.00 71.06 0.00 0.00 0.00 0.00
i-Butane 0.00 29.44 29.44 29.44 16.19 29.28 0.00
n-Butane 0.00 34.41 34.41 34.41 18.65 33.72 0.00
i-Butene 0.00 8.27 8.27 8.27 4.53 8.19 0.00
1-Butene 0.00 90.95 90.95 44.94 24.61 44.49 0.00
1-Hexene 0.00 0.14 0.14 21.21 0.12 0.21 0.00
1-Heptene 0.00 0.00 0.00 26.53 0.00 0.00 0.00
1-Octene 0.00 0.00 0.00 7.41 0.00 0.00 0.00
1-Undecene 0.00 0.00 0.00 2.34 0.00 0.00 0.00
Stream Number 8 9 10 11 12 13 14
Temperature (oC) 151 78 78 135 107 107 154
Pressure (bar) 5.8 4.5 4.5 2.5 4.0 4.0 2.0
Vapor fraction 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Mass flow (tonne/h) 5.64 5.79 1.86 3.79 4.30 2.53 1.26
Mole flow (kmol/h) 58.65 69.84 22.44 36.22 43.78 25.76 10.46
Component flowrates
(kmol/h)
Propane 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Propylene 0.00 0.00 0.00 0.00 0.00 0.00 0.00
i-Butane 0.16 0.50 0.16 0.00 0.00 0.00 0.00
n-Butane 0.69 2.15 0.69 0.00 0.00 0.00 0.00
i-Butene 0.08 0.25 0.08 0.00 0.00 0.00 0.00
1-Butene 0.45 1.40 0.45 0.00 0.00 0.00 0.00
1-Hexene 21.00 64.70 20.79 0.21 0.36 0.21 0.00
1-Heptene 26.52 0.84 0.27 26.26 43.28 25.47 0.79
1-Octene 7.41 0.00 0.00 7.41 0.14 0.08 7.33
1-Undecene 2.34 0.00 0.00 2.34 0.00 0.00 2.34
Turton_AppB_Part1.qxd
5/11/12
Equipment P-1201 A/B P-1202 A-G* P-1203 A/B P-1204 A/B P-1205 A/B P-1206 A/B
MOC Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel
Power (shaft) 6.75 5.13 2.75 0.66 2.15 1.93
Page 141
(kW)
Efficiency 40% 70% 40% 40% 40% 40%
Type/drive Centrifugal/ Centrifugal/ Centrifugal/ Centrifugal/ Centrifugal/ Centrifugal/
electric electric electric electric electric electric
Temperature 25 45 45 151 78 107
(°C)
Pressure in 2.97 8.00 5.50 2.50 2.00 1.50
(bar)
Pressure out 9.00 9.00 7.55 4.00 4.47 4.00
(bar)
*Seven identical pumps: five operating + two spares.
(continued)
141
142
Turton_AppB_Part1.qxd
Internals — — — — —
Pressure 20.0 5.0 4.5 1.0 0.5
(barg)
Shell side
Max. temp 45 160 160 45 160 78
(oC)
Pressure 8.0 5.0 5.0 4.0 5.0 1.0
(barg)
Phase L Cond. steam Cond. steam Cond. vapor Cond. steam Cond. vapor
MOC Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel
Tube side
Max. temp 40 103 151 40 135 40
(oC)
Pressure 3.0 6.7 4.8 3.0 1.5 3.0
(barg)
Phase L L+V Boiling liq. L Boiling liq. L
MOC Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel
*Area and duty given for one exchanger; five identical exchangers are needed.
(continued)
143
144
Turton_AppB_Part1.qxd
5/11/12
Shell side
Max. temp 78 160 107 107 154
(oC)
Pressure 1.0 5.0 0.5 0.3 0.7
(barg)
Phase L Cond. steam Cond. vapor L L
MOC Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel
Tube side
Max. temp 40 154 40 40 40
(oC)
Pressure 3.0 1.0 3.0 3.0 3.0
(barg)
Phase L Boiling liq. L L L
MOC Carbon steel Carbon steel Carbon steel Carbon steel Carbon steel
Turton_AppB_Part1.qxd
5/11/12
12:22 AM
145
Turton_AppB_Part1.qxd 5/11/12 12:22 AM Page 146
146 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
In order to maximize the selectivity of the heptene reaction, several reactor configura-
tions were considered [1]. The reactor configuration that maximized the heptene produc-
tion, in a minimum volume, was found to be a plug flow reactor in which the butene
feed was introduced at one end and the propylene stream was injected along the side of
the reactor. However, due to other considerations such as reactor complexity, it was
finally decided to use a reactor with five equal stages in which the concentration in each
stage is maintained approximately the same. Heat removal and mixing in each stage are
accomplished by withdrawing a stream of material and pumping it through an external
heat exchanger and back into the same stage of the reactor. The liquid cascades down-
ward from stage to stage by means of liquid downcomers. The inside of the reactor can
thus be considered similar to a five-plate distillation column (without vapor flow). The
distribution of the feeds into the different stages is not shown in Figure B.11.1, and the
dimensions of the reactor are taken directly from Chauvel et al. [1].
B.11.4 Reference
1. Chauvel, A., P. Leprince, Y. Barthel, C. Raimbault, and J-P Arlie, Manual
of Economic Analysis of Chemical Processes, trans. R. Miller and E. B. Miller (New York:
McGraw-Hill, 1976), 207–228.
The water-gas shift (WGS) reaction has been traditionally used to produce hydrogen from
syngas, which comprises CO and H2. This process can also be used for producing com-
bustion gas with lower levels of carbon from a carbon-rich syngas. The shift reaction is
mildly exothermic and equilibrium limited. Therefore, the extent of reaction becomes lim-
ited as the temperature increases along the length of the reactor. A two-stage process with
interstage cooling is used to achieve the desired extent of conversion. A higher tempera-
ture results in a higher reaction rate, and a chromia-promoted iron oxide catalyst is used
in the first stage. The second stage operates at a comparatively lower temperature, where
a copper-zinc catalyst is used. The main reaction is
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 147
Bulk density = 1121 kg/m3 for the first bed with iron catalyst
= 1442 kg/m3 for copper-zinc catalyst
In this process, the steam/CO ratio can be manipulated to affect the CO conversion.
The optimum values can be determined by an economic analysis. A higher steam/CO
ratio may result in a shorter overall reactor length and less residual CO, but it adds to the
cost due to the use of steam and a larger diameter of the reactor(s) to accommodate the
larger flowrate. Table B.12.1 shows stream data for a process using a steam/CO ratio of 3
(molar basis).
148
Syngas First-Stage Interstage Second-Stage Low-Pressure Reactor Shifted
Turton_AppB_Part2.qxd
FIC
5/11/12
4 5
Steam
poc
12:20 AM
9
FIC
H-1301 Shifted
50 Syngas
1 2
3 12.8
Page 148
Syngas
6 V-1301
air ng
LIC
R-1301
E-1303
10
7 Condensate to
185
Wastewater
E-1301 13.2
Tr eatment Unit
203
14.2 E-1302
R-1302
T (°C)
P (bar)
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 149
Stream Number 1 3 4 6
Temperature (°C) 115 320 325 319.7
Pressure (bar) 16.7 15.2 16.2 15.2
Vapor fraction 1.0 1.0 1.0 1.0
Mass flow (kg/h) 2191.2 2191.2 1678.3 3869.5
Mole flow (kmol/h) 100.0 100.0 93.2 193.2
Component flowrates (kmol/h)
CO 31.3 31.3 0.0 31.3
CO2 27.7 27.7 0.0 27.7
H2 40.2 40.2 0.0 40.2
H2O 0.8 0.8 93.2 94.0
Stream Number 7 8 9 10
Temperature (°C) 425.1 250.1 50 50
Pressure (bar) 14.7 13.8 12.7 11.7
Vapor fraction 1.0 1.0 1.0 0.0
Mass flow (kg/h) 3869.5 3869.5 2705.0 1164.5
Mole flow (kmol/h) 193.2 193.2 128.6 64.6
Component flowrates (kmol/h)
CO 11.6 3.1 3.1 0.0
CO2 47.4 55.9 55.9 0.0
H2 59.9 68.4 68.4 0.0
H2O 74.3 65.8 1.2 64.6
150 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
E-1303
A = 62.2 m2
Floating head, carbon steel, shell-and-tube design
Process stream in shell
Q = 3764 MJ/h
Maximum pressure rating of 19 bar
Reactors
R-1301 R-1302
Carbon steel, chromia-promoted iron oxide catalyst Carbon steel, copper-zinc oxide catalyst
Catalyst bed height = 2.8 m Catalyst bed height = 1.9 m
Diameter = 0.75 m Diameter = 0.75 m
Maximum pressure rating of 19 bar Maximum pressure rating of 19 bar
Maximum allowable catalyst temperature = 477°C Maximum allowable catalyst temperature = 288°C
Vessel
V-1301
Vertical
Carbon steel
Length = 1.83 m
Diameter = 0.61 m
Maximum pressure rating of 19 bar
Fired Heater
H-1301
Vertical
Required heat load = 696 MJ/h
Design (maximum) heat load = 800 MJ/h
75% thermal efficiency
Maximum pressure rating of 19 bar
B.12.4 Reference
1. Rase, H. F., Chemical Reactor Design for Process Plants, Vol. 2: Case Studies and De-
sign Data (New York: John Wiley and Sons, 1977).
CO2 capture and sequestration from coal-derived syngas is being strongly considered to
reduce environmental pollution. Because of a number of advantages, such as lower
solvent loss, higher selectivity toward H2S, better thermal stability, better water solubility,
Turton_AppB_Part2.qxd 5/11/12 12:20 AM Page 151
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 151
and lower circulation rate [1], dimethyl ether of polyethylene glycol (DEPG, Selexol) is
very suitable for selective capture of CO2 and H2S when the partial pressure of these acid
gases is high.
9
FIC Clean
refrg
Syngas
10 4.4 22.1 P-1402
12:20 AM
MP CO2
T-1402
P-1404
FIC
E-1402 5
refrg LP CO2
V-1401
E-1407 2
7
4.4 LIC 4
Page 152
refrg
V-1402
T-1401 3 LIC
E-1401 6
Sour air P-1401
Syngas 70 22.1
LIC
H2S Rich Gas
1 111 E-1405
8 to Claus Unit
1.25
E-1404 14
LIC
11 cw
12
C-1401
T-1403
16 V-1404 LIC
FIC
17 E-1403
V-1403 Sour
Water
P-1403
170
19 15
Makeup
Solvent
LIC
FIC hps
Nitrogen
13 E-1406
20
Solvent
Purge
18
High-Pressure FIC
Steam
o
Te mperature, C
21
Pressure, bar
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 153
block maintains the H2S concentration in Stream 14 by manipulating the operating pres-
sure of V-1403. This flowsheet contains a number of recycle streams along with the design
blocks. In addition, considerable mass and heat integration exists. Therefore, an appropri-
ate solution strategy must be considered to avoid convergence failure. In Section 16.3 a
number of approaches to solve such problems were outlined. The equation-oriented (EO)
method is suggested for this problem where a few iterations can be performed using the
sequential modular approach to generate a reasonable initial guess.
In Table B.13.3, it can be noted that the duty of heat exchanger E-1403 is very high.
Consequently, a large heat-exchange area is calculated. Usually, a proprietary, plate-type
heat exchanger is used for this service, which can provide a very high heat-exchange area
and achieve a temperature approach as low as 5°C. This can significantly reduce the
duties of E-1406 and E-1407.
It should be noted that Stream 5 contains a high amount of H2. To recover the H2,
the solvent can be flashed in a vessel that operates at a higher pressure than V-1401, and
H2 can be recycled to T-1402. This introduces another recycle stream. For simplicity, this
option is not considered here. Interested students are encouraged to implement this
option for H2 recovery.
Stream Number 1 2 3 4 5
Temperature (°C) 20.1 7.2 10.8 11.3 9.7
Pressure (bar) 21.4 20.7 23.4 5.1 5.1
Vapor fraction 1.0 1.0 0.0 0.02 1.0
Mass flow (tonne/h) 104.6 123.8 729.1 2209.5 9.62
Mole flow (kmol/h) 5389.0 5888.1 4490.4 13,607.8 270.5
Component flowrates
(kmol/h)
Selexol 0.0 0.0 2430.0 7364.0 0.0
CO 28.8 29.2 0.3 1.0 0.8
CO2 1114.0 1495.8 446.3 1352.5 187.9
H2 2468.8 2481.9 13.1 39.8 36.6
H2O 23.1 4.4 1583.3 4798.1 0.8
N2 1605.1 1818.3 14.8 44.9 39.4
AR 33.0 34.8 1.3 3.7 2.3
CH4 48.0 49.2 1.3 3.8 2.7
NH3 1.1 0.0 0.0 0.0 0.0
4 5 4
(1.4 × 10 ) (9.2 × 10 ) (2.8 × 10 ) (6.7 × 106)
H2S 67.1 0.0 0.0 0.0 0.0
4
(7.9 × 10 ) 4
(5.5 × 10 ) 3
(1.7 × 10 ) (3.2 × 105)
*Whenever NH3 and H2S flows are low, they are provided inside parentheses for tracking these
species through the flowsheet mainly because these species are maintained at a very low level
(ppm level) in the clean gas.
(continued)
Turton_AppB_Part2.qxd 5/11/12 12:20 AM Page 154
154 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
Stream Number 6 7 8 9 10
Temperature (°C) 9.7 6.1 6.1 8.2 5.2
Pressure (bar) 5.1 1.5 1.5 20.0 21.7
Vapor fraction 0.0 1.0 0.0 1.0 0.0
Mass flow (tonne/h) 2199.8 28.5 2171.4 66.7 709.04
Mole flow (kmol/h) 13,337.3 655.8 12,681.5 4516.1 4019.2
Component flowrates
(kmol/h)
Selexol 7364.0 0.0 7364.0 0.0 2430.0
CO 0.2 0.2 0.0 27.9 0.0
CO2 1164.6 638.7 525.9 222.8 0.0
H2 3.2 3.2 0.0 2429.0 0.0
H2O 4797.3 6.0 4791.3 3.5 1589.2
N2 5.5 5.4 0.1 1758.7 0.0
AR 1.4 1.3 0.1 30.0 0.0
CH4 1.1 1.0 0.1 44.2 0.0
NH3 0.0 0.0 0.0 0.0 0.0
(2.7 × 104) (4.2 × 105) (2.29 × 104) (1.4 × 106) (5.0 × 1011)
H2S 0.0 0.0 0.0 0.0 0.0
(1.6 × 103) (2.0 × 104) (1.4 × 103) (5.1 × 106) (2.3 × 108)
Stream Number 11 12 13 14 15
Temperature (°C) 12.0 169.3 169.3 50.0 50.0
Pressure (bar) 20.8 10.0 10.0 1.2 5.0
Vapor fraction 0.0 1.0 0.0 1.0 0.0
Mass flow (tonne/h) 738.0 29.2 714.5 5.45 1.54
Mole flow (kmol/h) 4753.8 787.9 4165.9 148.9 85.2
Component flowrates
(kmol/h)
Selexol 2434.2 4.2 2430.0 0.0 0.0
CO 0.3 0.3 0.0 0.0 0.0
CO2 459.7 395.1 64.6 64.5 0.0
H2 13.4 13.4 0.0 0.0 0.0
H2O 1654.5 52.5 1602.0 15.2 85.1
N2 13.6 212.0 0.9 0.9 0.0
AR 1.3 1.8 0.2 0.2 0.0
CH4 1.3 1.3 0.0 0.0 0.0
NH3 3.5 2.4 1.1 1.1 0.0 (0.013)
H2S 172.0 104.9 67.1 67.0 0.0 (0.081)
Turton_AppB_Part2.qxd 5/11/12 12:20 AM Page 155
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 155
Stream Number 16 17 18 19 20 21
Temperature (°C) 50.0 49.0 49.0 30.0 100.0 160.0
Pressure (bar) 1.3 1.2 1.2 1.5 20.0 6.0
Vapor fraction 0.0 0.0 0.0 0.0 1.0 1.0
Mass flow (kg/h) 2.11 709.1 1.5 1.4 5.61 1.63
Mole flow (kmol/h) 117.1 4022.5 8.3 5.0 200.0 90.7
Component flowrates
(kmol/h)
Selexol 0.0 2430.0 5.0 5.0 0.0 0.0
CO 0.0 0.0 0.0 0.0 0.0 0.0
CO2 0.0 0.0 0.0 0.0 0.0 0.0
H2 0.0 0.0 0.0 0.0 0.0 0.0
H2O 116.9 1593.0 3.3 0.0 0.0 90.7
N2 0.0 0.0 0.0 0.0 199.2 0.0
AR 0.0 0.0 0.0 0.0 0.8 0.0
CH4 0.0 0.0 0.0 0.0 0.0 0.0
NH3 0.0 0.0 0.0 0.0 0.0 0.0
11 13
(0.017) (5.0 × 10 ) (1.0 × 10 )
H2S 0.1 0.0 0.0 0.0 0.0 0.0
8 11
(2.4 × 10 ) (4.8 × 10 )
(continued)
Turton_AppB_Part2.qxd 5/11/12 12:20 AM Page 156
Pumps
P-1401 P-1402
Centrifugal Centrifugal
Carbon steel Carbon steel
Actual power = 85.2 kW Actual power = 1485.1 kW
Efficiency 75% Efficiency 78%
P-1403 P-1404
Centrifugal Centrifugal
Carbon steel Carbon steel
Actual power = 0.7 kW Actual power = 505.0 kW
Efficiency 70% Efficiency 75%
Towers
T-1401 T-1402
Carbon steel Carbon steel
12 valve trays 13 valve trays
24-in tray spacing 24-in tray spacing
Column height = 18.0 m Column height = 25.0 m
Diameter = 3.0 m Diameter = 5.2 m
Maximum pressure rating of 26 bar Maximum pressure rating of 25 bar
T-1403
Carbon steel
8 valve trays plus reboiler and condenser
24-in tray spacing
Column height = 16.2 m
Diameter = 3.6 m
Maximum pressure rating of 8 bar
156
Turton_AppB_Part2.qxd 5/11/12 12:20 AM Page 157
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 157
B.13.3 References
1. Bhattacharyya, D., R. Turton, and S. E. Zitney, “Steady State Simulation and Opti-
mization of an Integrated Gasification Combined Cycle (IGCC) Plant with CO2 Cap-
ture,” Ind. Eng. Chem. Res. 50 (2011): 1674–1690.
2. Gross, J., and G. Sadowski, “Perturbed-Chain SAFT: An Equation of State Based on
a Perturbation Theory for Chain Molecules,” Ind. Eng. Chem. Res. 40 (2001):
1244–1260.
3. Aspen Plus Model of the CO2 Capture Process by Selexol, 2008, pp. 1–22; www.as-
pentech.com.
4. Xu, Y., R. P. Schutte, and L. G. Hepler, “Solubilities of Carbon Dioxide, Hydrogen
Sulfide and Sulfur Dioxide in Physical Solvents,” Can. J. Chem. Eng. 70 (1992):
569–573.
The Claus process is one of the most common processes for sulfur recovery from acid
gases generated in oil and gas refining. The Claus unit is designed to recover sulfur from
the acid gas recovered from an acid-gas removal (AGR) unit and the sour gas produced
from a sour-water stripper (SWS).
158 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
gasification combined cycle (IGCC) power plant. Efficient design of a Claus process de-
pends upon high recovery of sulfur and complete destruction of other impurities such as
methane and ammonia [1–4]. It should be noted that elemental sulfur, in the operating
temperature range of the Claus unit, can exist as S2 and S8, among others. For simplicity,
only these two sulfur species will be considered.
Acid gas, Stream 2, from an acid-gas removal unit and sour-water gas, Stream 3,
from the sour-water stripper are preheated in E-1502 and E-1503, respectively, with high-
pressure steam and sent to the reaction furnace, H-1501, for combustion. Preheated,
enriched oxygen from an air separation unit (ASU) is used as the oxidant in H-1501.
Within the furnace, incomplete combustion of hydrogen sulfide to sulfur dioxide is
carried out. Additionally, partial combustion of ammonia can also take place. It is desired
that only one-third of the hydrogen sulfide contained in the gases be combusted to form a
2/1 ratio of hydrogen sulfide to sulfur dioxide. This 2/1 ratio of hydrogen sulfide to
sulfur dioxide is required to maximize sulfur yield in the downstream reactors. Primary
combustion reactions within H-1501 are
3 k1
H2S + O2 ¡ SO2 + H2O (B.14.1)
2
3 k2 1 3
NH3 + O2 ¡ N2 + H2O (B.14.2)
4 2 2
These highly exothermic reactions increase the temperature substantially (to about
1450°C) in H-1501. Several side reactions take place. The side reaction shown in Equation
(B.14.6) destroys any ammonia not combusted in Reaction (B.14.2).
k3
H2S + SO2 + H2 Δ S2 + 2H2O (B.14.3)
k4 1
H2S Δ S + H2 (B.14.4)
2 2
k5
CO2 + H2 Δ CO + H2O (B.14.5)
3 k6 1 3 3
NH3 + SO2 ¡ N2 + H2O + S2 (B.14.6)
4 2 2 8
The hot process gas is then cooled in E-1504 to generate high-pressure steam and
to quench the reactions taking place. At high operating temperatures, such as those in
H-1501, sulfur exists primarily as S2. As the cooling takes place in E-1504, the equilibrium
shifts as shown in Equation B.14.7. Due to the equilibrium shift, the primary sulfur
species present at the outlet of E-1504 is S8.
k7 1
S2 ÷ S (B.14.7)
4 8
Further cooling is carried out in E-1505 by generating low-pressure steam. This
cooled process gas is then sent to V-1501 to separate the liquid sulfur. The process gas is
then sent to the first stage of a two-stage process. The process gas is heated in E-1506 with
high-pressure steam before being sent to the reactor R-1501, where hydrogen sulfide and
sulfur dioxide react in a 2/1 ratio to form elemental sulfur via Equation (B.14.8) (known
Turton_AppB_Part2.qxd 5/11/12 12:20 AM Page 159
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 159
as the Claus reaction). The reactor effluent is then cooled by generating low-pressure
steam in E-1507. The liquid sulfur is then removed in V-1502. The process gas is again
preheated in E-1508 with high-pressure steam. The heated gas is sent to the second-stage
catalytic reactor R-1502, where the reaction shown in Equation (B.14.8) takes place. The
reactor effluent is cooled in E-1509 using cooling water to condense the formed sulfur.
The process gas is then sent to a tail-gas treatment unit (not modeled here).
1 k8 3
H2S + SO2 Δ S + H2O (B.14.8)
2 16 8
dp p pc
-Ei a b
-ri = ko,i expc (B.14.9)
RT H2S NH3 O2
where i is the equation number (B.14, i), and
i Ei ko,i a b c
kcal/kmol
1 11,000 1.40 × 104 1 0 1.5
2 40,000 4.43 × 106 0 1 0.75
The units of ri are kmol/s/m3-reactor, the units of pi are atm, and the units of ko,i
vary depending upon the form of the equation.
The rate equations for the reactions in Equations (B.14.3) through (B.14.6) are [1]
4166 CCOCH2O
d aCCO2C0.5 d b (B.14.12)
-60.3
-r5 = 1.52 * 1012 expc H2 - expc -3.88 +
RT T C0.5
H2
dCNH3CSO2
-27.5 0.25 0.5
-r6 = 2.29 * 104 expc (B.14.13)
RT
The units of ri are kmol/s/m3-reactor, the units of pi are atm, and the units of Ci are
kmol/m3.
The temperature dependence of the equilibrium between S2 and S8 shown in Equa-
tion (B15.7) is given as [1]
Turton_AppB_Part2.qxd 5/11/12 12:21 AM Page 160
160 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
d
47,800
KP = expc -53.67 + (B.14.14)
T[K]
The reaction in Equation (B.14.7) is modeled in E-1504.
Equation (B.14.8) is catalyzed in R-1501 and R-1502 by either an alumina or a tita-
nium catalyst. Since Equation (B.14.8) is equilibrium limited and mildly exothermic, the
maximum allowable temperature of the catalyst is not a concern. However, significant
catalyst deactivation occurs when the temperature is lowered below the dew point of
sulfur, since the sulfur will deposit on the catalyst. For this reason, each reactor is operated
at a sufficiently high temperature to ensure that no sulfur condenses and deposits on the
catalyst. The rate equation for Equation (B.14.8) is [1]
dpH2Op0.1875
5550
pH2Sp0.5
SO2 - expc8.66 - S8
d± ≤
-7.35 T
-r8 = 5360 expc 2
(B.14.15)
a1 + 1.14 expc dpH2O b
RT -0.6
RT
The units of r8 are mol/s/kg-cat, and the units of pi are atm.
1 YC
12:21 AM
FIC E-1508
230
3
E-1503 hps 15
AGR Unit hps
Off-Gas To Tail-Gas
11
E-1506 240 Treatment
R-1502 Unit
hps mps 7 V-1502
E-1509
hps
4 5
V-1501 R-1501 V-1503
E-1504 12 13
E-1505 10
bfw bfw 9 cw
lps
LIC
14
6 8
T (°C) LIC E-1507 LIC
bfw
16
Sulfur to
Storage
161
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162 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
Stream Number 1 2 3 4
Temperature (°C) 32 120 50 345
Pressure (bar) 10.0 2.4 2.1 1.7
Vapor fraction 1.0 1.0 1.0 1.0
Mass flow (tonne/h) 3.01 2.2 14.4 19.6
Mole flow (kmol/h) 94.7 85.9 388.1 553.9
Component flowrates
(kmol/h)
Hydrogen sulfide 0.0 23.9 159.1 40.3
Sulfur dioxide 0.0 0.0 0.0 20.1
Water 0.0 0.0 15.6 203.5
Carbon dioxide 0.0 16.9 174.1 142.8
Carbon monoxide 0.0 2.1 0.0 50.3
Oxygen 90.0 0.0 0.0 0.0
Hydrogen 0.0 10.2 0.0 24.2
Nitrogen 4.7 1.3 31.3 57.1
Ammonia 0.0 31.6 7.9 0.0
S2 0.0 0.0 0.0 0.4
S8 0.0 0.0 0.0 15.2
Stream Number 5 6 7 8
Temperature (°C) 195 195 195 314
Pressure (bar) 1.6 1.6 1.6 1.3
Vapor fraction 0.97 0.0 1.0 1.0
Mass flow (tonne/h) 19.6 3.72 15.9 15.9
Mole flow (kmol/h) 553.8 15.3 538.5 529.4
Component flowrates
(kmol/h)
Hydrogen sulfide 40.3 0.0 40.3 11.1
Sulfur dioxide 20.1 0.0 20.1 5.5
Water 203.5 0.7 202.8 232.0
Carbon dioxide 142.8 0.0 142.8 142.8
Carbon monoxide 50.3 0.0 50.3 50.3
Oxygen 0.0 0.0 0.0 0.0
Hydrogen 24.2 0.0 24.2 24.2
Nitrogen 57.1 0.0 57.1 57.1
Ammonia 0.0 0.0 0.0 0.0
S2 0.2 0.2 0.0 0.1
S8 15.3 14.4 0.9 6.3
Turton_AppB_Part2.qxd 5/11/12 12:21 AM Page 163
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 163
Stream Number 9 10 11 12
Temperature (°C) 175 175 175 234
Pressure (bar) 1.2 1.2 1.2 1.0
Vapor fraction 0.99 0.0 1.0 1.0
Mass flow (tonne/h) 15.9 1.51 14.4 14.4
Mole flow (kmol/h) 529.4 6.3 523.1 520.9
Component flowrates
(kmol/h)
Hydrogen sulfide 11.1 0.0 11.1 4.0
Sulfur dioxide 5.5 0.0 5.5 2.0
Water 232.0 0.4 231.6 238.8
Carbon dioxide 142.8 0.0 142.8 142.8
Carbon monoxide 50.3 0.0 50.3 50.3
Oxygen 0.0 0.0 0.0 0.0
Hydrogen 24.2 0.0 24.2 24.2
Nitrogen 57.1 0.0 57.1 57.1
Ammonia 0.0 0.0 0.0 0.0
S2 0.1 0.1 0.0 0.0
S8 6.3 5.8 0.5 1.8
Stream Number 13 14 15 16
Temperature (°C) 160 160 160 187
Pressure (bar) 0.9 0.9 0.9 0.9
Vapor fraction 1.0 0.0 1.0 0.0
Mass flow (tonne/h) 14.4 0.38 14.0 5.61
Mole flow (kmol/h) 520.9 1.6 519.3 23.15
Component flowrates
(kmol/h)
Hydrogen sulfide 4.0 0.0 4.0 0.0
Sulfur dioxide 2.0 0.0 2.0 0.0
Water 238.8 0.1 238.7 1.2
Carbon dioxide 142.8 0.0 142.8 0.0
Carbon monoxide 50.3 0.0 50.3 0.0
Oxygen 0.0 0.0 0.0 0.0
Hydrogen 24.2 0.0 24.2 0.0
Nitrogen 57.1 0.0 57.1 0.0
Ammonia 0.0 0.0 0.0 0.0
S2 0.0 0.0 0.0 0.3
S8 1.8 1.5 0.4 21.7
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164 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 165
Reaction Furnace
R-1501A R-1501B
Furnace (flame zone) Furnace (anoxic zone)
Refractory lined Refractory lined
Length = 0.5 m Length = 4.7 m
Diameter = 2.5 m Diameter = 2.5 m
Design pressure = 2 bar Design pressure = 2 bar
Reactors
R-1501 R-1502
Carbon steel Carbon steel
Packed bed filled with catalyst Packed bed filled with catalyst
Diameter = 1.22 m Diameter = 1.22 m
Height = 1.92 m Height = 1.92 m
Maximum pressure rating of 2 bar Maximum pressure rating of 2 bar
Vessels
V-1501 V-1502
Horizontal Horizontal
Carbon steel Carbon steel
Length = 6.80 m Length = 5.06 m
Diameter = 2.27 m Diameter = 1.69 m
Maximum pressure rating of 2 bar Maximum pressure rating of 2 bar
V-1503
Horizontal
Carbon steel
Length = 5.29 m
Diameter = 1.76 m
Maximum pressure rating of 2 bar
B.14.4 References
1. Jones, D., D. Bhattacharyya, R. Turton, and S. E. Zitney, “Rigorous Kinetic Modeling
and Optimization Study of a Modified Claus Unit for an Integrated Gasification
Combined Cycle (IGCC) Power Plant with CO2 Capture,” Ind. Eng. Chem. Res.,
dx.doi.org/10.1021/ie201713n (2012).
2. Monnery, W. D., K. A. Hawboldt, A. Pollock, and W. Y. Svrcek, “New Experimental
Data and Kinetic Rate Expression for the Claus Reaction,” Chemical Engineering Sci-
ence 55 (2000): 5141–5148.
3. Hawboldt, K. A., “Kinetic Modeling of Key Reactions in the Modified Claus Plant
Front End Furnace,” Ph.D. thesis, Department of Chemical and Petroleum Engineer-
ing, University of Calgary, Canada, 1998.
4. Monnery, W. D., K. A. Hawboldt, A. E. Pollock, and W. Y. Svrcek, “Ammonia Pyrol-
ysis and Oxidation in the Claus Furnace,” Ind. Eng. Chem. Res. 40 (2001): 144–151.
5. Perry, R. H., and D. W. Green, eds., Perry’s Chemical Engineers’ Handbook, 7th ed.
(New York: McGraw-Hill, 1997).
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166 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
Gasifiers can be used for generating syngas from coal, petroleum coke (petcoke), biomass,
and similar feedstocks. In a gasifier, substoichiometric oxygen is provided to generate
syngas with a higher CO/CO2 ratio. Gasification reactions finally result in substantial
conversion of carbon (as high as 98% to 99%). There are various types of gasifiers. In this
project, a model of a downward-flow, oxygen-blown, entrained-flow gasifier will be
developed.
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 167
k4
C + 0.5O2 ¡ CO (B.15.5)
k5
C + CO2 ¡ 2CO (B.15.6)
k6
C + H2O ¡ CO + H2 (B.15.7)
Table B.15.1 Proximate and Ultimate Analysis of Illinois No. 6 Coal (as Received)
Proximate Ultimate
Coal Moisture VM FC Ash C H O N S
Illinois No. 6 5.86 34.03 50.52 9.59 68.51 4.54 6.98 1.49 3.03
168 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
The reaction kinetics for Reaction (B.15.2) is given by Westbrook and Dryer [2]:
bCO2 CCOC0.5
167,504 0.25 kmol
-rCO = 8.8 * 1011 expa - H2O (B.15.9)
RT m3 s
The reaction kinetics for Reaction (B.15.3) is given by Westbrook and Dryer [2]:
bCO2 CCH4 3
202,680 1.3 0.2 kmol
-rCH4 = 8.47 * 1010 expa - (B.15.10)
RT ms
The reaction kinetics for Reaction (B.15.4) is given by Jones and Lindstedt [3]:
bCH2 CO2
167,504 0.25 1.5 kmol
-rH2 = 2.72 * 1015T-1 expa - (B.15.11)
RT m3 s
For the char combustion reaction, Equation (B.15.5), the kinetics of the surface reac-
tions available in the open literature for a shrinking-core model [4] is used. For incorpo-
rating in a process simulator, the rate expression has been simplified by assuming that the
diffusive resistance in the ash layer is the dominating resistance to mass transfer. Further,
it is assumed that the char particles have a diameter of 400 µm, and the average operating
pressure of the gasifier is 24.5 atm. Subsequently, the reaction kinetics for Equation
(B.15.5) can be written as
byC yO2 3
113,070 2>3 kmol
-rC = 1.63 * 109 expa - (B.15.12)
RT m s
The kinetics for Equation (B.15.6) is given by Wen et al. [5]:
byCyCO2 3
175,880 kmol
-rC = 42,090 expa - (B.15.13)
RT ms
The kinetics for Equation (B.15.7) is given by Wen and Onozaki [5]:
byCyH2O 3
175,880 kmol
-rC = 42,090 expa - (B.15.14)
RT ms
The kinetics for Equation (B.15.8) is given by Wen and Onozaki [5]:
yCO2yH2 kmol
b ayCOyH2O - b
70,071
-rCO = 52.3 expa - (B.15.15)
RT Keq m3 s
In Equation (B.15.15),
d
4019
Keq = expc -3.689 + (B.15.16)
T
In the equations provided before, the activation energy is given in kJ/kmol, the
units of concentration are kmol/m3[[FR 3]] (gas), and T is in K whenever a specific unit is
needed.
Turton_AppB_Part2.qxd 5/11/12 12:21 AM Page 169
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 169
170 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
orders of magnitude to avoid convergence failure. This modification will have negligible
effect in the simulation results.
The stream data for the intermediate streams, Stream 51 and Stream 52, are pro-
vided in Table B.15.3. Since solids are included in this table and in Table B.15.4, mass
flowrates (instead of molar flowrates that are commonly reported in other examples) are
given.
Stream Number 51 52
Temperature (°C) 500 1050
Pressure (bar) 25.3 25.3
Mass flow (tonne/h) 100.0 233.0
Component flowrates
(tonne/h)
Coal 0.0 0.0
C 60.082 60.082
Ash 9.593 9.593
O2 0.0 40.796
CO 2.157 0.0
H2 1.027 0.0
CO2 1.196 30.834
H2O 11.349 82.018
H2S 3.221 3.221
N2 0.0 4.650
CH4 9.569 0.0
NH3 1.806 1.806
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FT FIC
12:21 AM
3
Oxygen
Page 171
FT
1
Coal
remote
RC set point R-1601
FT FIC
2
Water 4
Gasifier
Effluent
Figure B.15.1 Unit 1600: Flow Diagram of a Downward-Flow, Oxygen-Blown, Entrained-Flow Gasifier
171
172
FT
Turton_AppB_Part2.qxd
3
Oxygen
5/11/12
FT
1
Coal
12:21 AM
R-1601A
Page 172
51
2
R-1601B
Water
52
R-1601C
4
Gasifier
Effluent
Figure B.15.2 Unit 1600: Multizonal Approach for Modeling a Downward-Flow, Oxygen-Blown, Entrained-Flow Gasifier (Instrumentation
Lines Not Shown) (Note: This is not a process flow diagram; it is a representation of the simulation strategy.)
Turton_AppB_Part2.qxd 5/11/12 12:21 AM Page 173
Appendix B Information for the Preliminary Design of Fifteen Chemical Processes 173
Stream No. 1 2 3 4
Temperature (°C) 40 40 50 1143
Pressure (bar) 25.3 26.3 26.3 24.3
Mass flow (tonne/h) 100.0 40.0 93.0 233.0
Component flowrates
(tonne/h)
Coal 100.0 0.0 0.0 0.0
C 0.0 0.0 0.0 3.237
Ash 0.0 0.0 0.0 9.593
O2 0.0 0.0 88.350 0.0
CO 0.0 0.0 0.0 119.805
H2 0.0 0.0 0.0 5.319
CO2 0.0 0.0 0.0 50.884
H2O 0.0 40.0 0.0 34.485
H2S 0.0 0.0 0.0 3.221
N2 0.0 0.0 4.650 4.650
CH4 0.0 0.0 0.0 0.0
NH3 0.0 0.0 0.0 1.806
174 Appendix B Information for the Preliminary Design of Fifteen Chemical Processes
B.15.4 References
1. Syamlal, M., and L. A. Bissett, “METC Gasifier Advanced Simulation (MGAS)
Model,” Technical Note, NITS Report No. DOE/METC-92/4108, 1992.
2. Westbrook, C. K., and F. L. Dryer, “Simplified Mechanism for the Oxidation of
Hydrocarbon Fuels in Flames,” Combustion Sci. Tech. 27 (1981): 31–43.
3. Jones, W. P., and R. P. Lindstedt, “Global Reaction Schemes for Hydrocarbon Com-
bustion,” Combustion and Flame 73 (1988): 233–249.
4. Wen, C. Y., and T. Z. Chaung, “Entrainment Coal Gasification Modeling,” Ind. Eng.
Chem Process Des. Dev. 18 (1979): 684–695.
5. Wen, C. Y., H. Chen, and M. Onozaki, “User’s Manual for Computer Simulation and
Design of the Moving Bed Coal Gasifier,” DOE/MC/16474-1390, 1982.